U.S. patent number 7,204,861 [Application Number 10/859,479] was granted by the patent office on 2007-04-17 for hair coloring compositions.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Colin John Clarke, Jennifer Mary Marsh.
United States Patent |
7,204,861 |
Marsh , et al. |
April 17, 2007 |
Hair coloring compositions
Abstract
The present invention relates to hair colouring and bleaching
compositions comprising i) at least one source of
peroxymonocarbonate ions, ii) at least one alkalizing agent,
preferably a source of ammonium ions, and iii) at least one radical
scavenger, wherein said composition has a pH of up to 9.5, which
provide a high level of lift and lightening and the required dye
deposition and grey coverage whilst reducing the concentration of
peroxide, the ammonia odour and reducing the hair fibre damage.
Inventors: |
Marsh; Jennifer Mary
(Henley-on-Thames, GB), Clarke; Colin John
(Twickenham, GB) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
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Family
ID: |
33155256 |
Appl.
No.: |
10/859,479 |
Filed: |
June 2, 2004 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20040237218 A1 |
Dec 2, 2004 |
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Foreign Application Priority Data
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Jun 2, 2003 [EP] |
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03253447 |
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Current U.S.
Class: |
8/405; 8/567;
8/569; 8/570; 8/594; 8/602; 8/607; 8/688 |
Current CPC
Class: |
A61K
8/22 (20130101); A61K 8/347 (20130101); A61K
8/41 (20130101); A61K 8/44 (20130101); A61K
8/60 (20130101); A61Q 5/10 (20130101) |
Current International
Class: |
A61K
8/00 (20060101) |
Field of
Search: |
;8/101,107,111,405,567,569,570,594,602,607,688 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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29613065 |
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Jul 1996 |
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DE |
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435012 |
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Apr 1994 |
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EP |
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1106166 |
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Jun 2001 |
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EP |
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0840593 |
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Oct 2002 |
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EP |
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11-139941 |
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May 1999 |
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JP |
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11-343219 |
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Dec 1999 |
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JP |
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2003/095879 |
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Apr 2003 |
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JP |
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WO-01/28508 |
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Apr 2001 |
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WO |
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Other References
STIC Search Report dated Dec. 19, 2006. cited by examiner.
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Primary Examiner: Elhilo; Eisa
Attorney, Agent or Firm: Dressman; Marianne Krasovec;
Melissa G. Rosnell; Tara M.
Claims
What is claimed is:
1. A hair coloring composition comprising i) at least one source of
peroxymonocarbonate ions, ii) at least one source of alkalizing
agent, and iii) at least one source of radical scavenger selected
from the group consisting of: A. selected from compounds according
to the formula (I): R.sup.1--Y.sup.13
C(H)(R.sup.3)--R.sup.4--(C(H)(R.sup.5)--Y--R.sup.6).sub.n (I):
wherein Y Is NR.sub.2, O, or S; n is 0 to 2; and wherein R.sup.4 is
monovalent or divalent and is selected from: (a) substituted or
unsubstituted, straight or branched, alkyl, mono- or
poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or
heteroolefinic systems, (b) substituted or unsubstituted, mono- or
poly-cyclic aliphatic, aryl, or heterocyclic systems, or (c)
substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl
systems; the systems of (a), (b) and (C) comprising from about 1 to
about 12 carbon atoms and about 0 to about 5 heteroatoms selected
from the group consisting of O, S, N, P, and Si; and wherein
R.sup.4 can be connected to R.sup.3 or R.sup.5 to create a 5, 6 or
7 membered ring; and wherein R.sup.1, R.sup.2, R.sup.3, R.sup.5,
and R.sup.6 are monovalent and are selected independently from:
(a), (b), (c) or H; B. compounds according to the formula (II):
##STR00010## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5
are independently selected from H, COO-M+, Cl, Br, SO.sub.3-M+,
NO.sub.2, OCH.sub.3, OH or a C.sup.1 to C.sup.10 primary or
secondary alkyl and M is either H or alkali metal, or mixtures
thereof; and C. compounds selected from the group consisting of
benzylamine, imidazole, di-tert-butylhydroxytoluene, hydroquinone,
guanine, pyrazine, piperidine, morpholine, methylmorpholine,
2-methyoxyethylamine, and mixtures thereof, wherein said
composition has a pH of up to and including about 9.5.
2. A hair coloring composition according to claim 1, wherein said
source of peroxymonocarbonate ions comprises at least one source of
hydrogen peroxide and at least one source of ions selected from the
group consisting of carbonate ions, carbamate ions, hydrocarbonate
ions and mixtures thereof.
3. A hair coloring composition according to claim 1, wherein said
source of alkalizing agent is a source of ammonium ions.
4. A hair coloring composition according to claim 1, wherein said
composition has a pH of from about 7.5 to about 9.5.
5. A hair coloring composition according to claim 2, wherein said
composition comprises i. from about 0.1% to about 10% by weight of
hydrogen peroxide ii. from about 0.1 to about 10% by weight of said
alkalizing agent iii. from about 0.1 to about 15% by weight of said
source of carbonate ions, carbamate ions, hydrogencarbonate ions,
or mixtures thereof, and iv. from about 0.1% to about 10% by weight
of said radical scavenger.
6. A hair coloring composition according to claim 2, wherein said
composition comprises i. from about 1% to about 7% by weight of
hydrogen peroxide ii. from about 0.5 to about 5% by weight of said
alkalizing agent iii. from about 1% to about 8% by weight of said
source of carbonate ions, carbamate ions, hydrogencarbonate ions,
or mixtures thereof iv. from about 1% to about 7% by weight of said
radical scavenger.
7. A hair coloring composition according to claim 2, wherein said
source of alkalizing agent is a source of ammonium ions, and
wherein the weight ratio of said ammonium ion to said carbonate ion
is from about 3:1 to about 1:10.
8. A hair coloring composition according to claim 2, wherein the
weight ratio of said radical scavenger to said carbonate ion is
from about 2:1 to about 1:4.
9. A hair coloring composition according to claim 1, wherein said
radical scavenger is selected from the group consisting of
alkanolamines, amino sugars, amino acids, esters of amino acids,
and mixtures thereof.
10. A hair coloring composition according to claim 1, wherein said
radical scavenger is selected from the group consisting of
monoethanolamine, 3-amino-1-propanol, 4-amino-1-butanol,
5-amino-1-pentanol, 1-amino-2-propanol, 1-amino-2-butanol,
1-amino-2-pentanol, 1-amino-3-pentanol, 1-amino4-pentanol,
3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol,
3-aminopropane-1 ,2-diol, glucosamine, N-acetylglucosamine,
glycine, glutamic acid, arginine, lysine, proline, glutamine,
histidine, sarcosine, serine, tryptophan and potassium, sodium and
ammonium salts thereof, and mixtures thereof.
11. A hair coloring composition according to claim 1, wherein said
radical scavenger is selected from glucosamine, glycine, glutamic
acid, sarcosine, lysine, serine, 2-methoxyethylamine, morpholine,
piperidine, ethylamine, 3-amino-1-propanol and mixtures
thereof.
12. A hair coloring kit comprising a) an individually packaged
oxidizing component comprising at least one source of hydrogen
peroxide b) an individually packaged coloring component comprising:
i. at least one source of radical scavenger selected from the group
consisting of: A. selected from compounds according to the formula
(I):
R.sup.1--Y--C(H)(R.sup.3)--R.sup.4--(C(H)(R.sup.5)--Y--R.sup.6).sub.n
(I): wherein Y is NR.sub.2, O, or S; n is 0 to 2; and wherein
R.sup.4 is monovalent or divalent and is selected from: (a)
substituted or unsubstituted, straight or branched, alkyl, mono- or
poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or
heteroolefinic systems, (b) substituted or unsubstituted, mono- or
poly-cyclic aliphatic, aryl, or heterocyclic systems, or (C)
substituted or unsubstituted, mono-, poly., or per-fluoro alkyl
systems; the systems of (a), (b) and (c) comprising from about 1 to
about 12 carbon atoms and about 0 to about 5 heteroatoms selected
from the group consisting of O, S, N, P, and Si; and wherein
R.sup.4 can be connected to R.sup.3 or R.sup.5 to create a 5, 6 or
7 membered ring; and wherein R.sup.1, R.sup.2, R.sup.3, R.sup.5,
and R.sup.6 are monovalent and are selected independently from:
(a), (b), (c) or H; B. compounds according to the formula (II):
##STR00011## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5
are independently selected from H, COO-M+, Cl, Br, SO.sub.3-M+,
NO.sub.2, OCH.sub.3, OH or a C.sup.1 to C.sup.10 primary or
secondary alkyl and M is either H or alkali metal, or mixtures
thereof; and C. compounds selected from the group consisting of
benzylamine, imidazole, di-tert-butylhydroxytoluene, hydroquinone,
guanine, pyrazine, piperidine, morpholine, methylmorpholine,
2-methyoxyethylamine and mixtures thereof, ii. at least one source
of ions selected from the group consisting of carbonate ions,
carbamate ions, and hydrocarbonate ions; and iii. at least one
alkalizing agent.
13. A method of treating hair comprising the step of applying to
said hair for a time period a composition comprising: i. at least
one source of peroxymonocarbonate ions; ii. at least one alkalizing
agent; and iii. at least one source of radical scavenger selected
from the group consisting of: A. selected from compounds according
to the formula (I):
R.sup.1--Y--C(H)(R.sup.3)--R.sup.4--(C(H)(R.sup.5)--Y--R.sup.6).sub.n
(I): wherein Y is NR.sub.2, O, or S; n is 0 to 2; and wherein
R.sup.4 is monovalent or divalent and is selected from: (a)
substituted or unsubstituted, straight or branched, alkyl, mono- or
poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or
heteroolefinic systems, (b) substituted or unsubstituted, mono- or
poly-cyclic aliphatic, aryl, or heterocyclic systems, or (C)
substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl
systems; the systems of (a), (b) and (c) comprising from about 1 to
about 12 carbon atoms and about 0 to about 5 heteroatoms selected
from the group consisting of O, S, N, P, and Si; and wherein
R.sup.4 can be connected to R.sup.3 or R.sup.5 to create a 5, 6 or
7 membered ring; and wherein R.sup.1, R.sup.2, R.sup.3, R.sup.5,
and R.sup.6 are monovalent and are selected independently from:
(a), (b), (c) or H; B. compounds according to the formula (II):
##STR00012## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5
are independently selected from H, COO-M+, Cl, Br, SO.sub.3-M+,
NO.sub.2, OCH.sub.3, OH or a C.sup.1 to C.sup.10 primary or
secondary alkyl and M is either H or alkali metal, or mixtures
thereof; and C. compounds selected from the group consisting of
benzylamine, imidazole, di-tert-butylhydroxytoluene, hydroquinone,
guanine, pyrazine, piperidine, morpholine, methylmorpholine,
2-methyoxyethylamine, and mixtures thereof, wherein said
composition has a pH of up to about 9.5 for at least about 50% of
the time period said composition is applied and retained on the
hair.
14. A method of treating hair comprising the steps of (a) applying
a composition comprising at least one source of radical scavenger
selected from the group consisting of; and A. selected from
compounds according to the formula (I):
R.sup.1--Y--C(H)(R.sup.3)--R.sup.4--(C(H)(R.sup.5)--Y--R.sup.6).sub.n
(I): wherein Y is NR.sub.2, O, or S; n is 0 to 2; and wherein
R.sup.4 is monovalent or divalent and is selected from: (a)
substituted or unsubstituted, straight or branched, alkyl, mono- or
poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or
heteroolefinic systems, (b) substituted or unsubstituted, mono- or
poly-cyclic aliphatic, aryl, or heterocyclic systems, or (c)
substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl
systems; the systems of (a), (b) and (c) comprising from about 1 to
about 12 carbon atoms and about 0 to about 5 heteroatoms selected
from the group consisting of O, S, N, P, and Si; and wherein
R.sup.4 can be connected to R.sup.3 or R.sup.5 to create a 5, 6 or
7 membered ring; and wherein R.sup.1, R.sup.2, R.sup.3, R.sup.5,
and R.sup.6 are monovalent and are selected independently from:
(a), (b), (c) or H; B. compounds according to the formula (II):
##STR00013## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5
are independently selected from H, COO-M+, Cl, Br, SO.sub.3-M+,
NO.sub.2, OCH.sub.3, OH or a C.sup.1 to C.sup.10 primary or
secondary alkyl and M is either H or alkali metal, or mixtures
thereof, and C. compounds selected from the group consisting of
benzylamine, irnidazole, di-tert-butylhydroxytoluene, hydroquinone,
guanine, pyrazine, piperidine, morpholine, methylmorpholine,
2-methyoxyethylamine, and mixtures thereof, (b) separately applying
an oxidizing hair coloring composition comprising at least one
source of peroxymonocarbonate ion and at least one source of
alkalizing agent; wherein said steps (a) and (b) are
interchangeable.
Description
FIELD OF THE INVENTION
The present invention relates to compositions for the bleaching and
colouration and of keratinous fibres.
BACKGROUND OF THE INVENTION
The permanent alteration of the colour of keratinous fibres, in
particular human hair, by the application of hair dyes is well
known. In order to provide the consumer with the hair colour and
the intensity of colour desired, a very complex chemical process is
utilized. Permanent hair dyeing formulations typically comprise
oxidative hair dye precursors, which can diffuse into the hair
through the cuticle and into the cortex where they can then react
with each other and suitable oxidising agents to form the end dye
molecules. Due to the larger size of these resultant molecules they
are unable to readily diffuse out of the hair during subsequent
washing with water and/or detergents; hence delivering a
consumer-desired permanency of colour. This reaction typically
takes place in an aggressive environment at approximately pH 10 in
the presence of an alkalizing agent and in the presence of an
oxidizing agent. Moreover, the consumer repeats this process
regularly in order to maintain the desired hair colour and shade
and the intensity of colour and to ensure continual, even coverage
of the hair including coverage of new hair growth.
The manufacturer of such products is also required to work within a
large number of constraints. Since these products are being placed
in direct contact with the consumers' skin, the potential exists
for accidental contact with the eye or for ingestion (for example),
which can occur during the dyeing process. Therefore, the
formulation must meet rigorous safety requirements and not induce
any allergic reactions. In addition to meeting these requirements,
the products must also be optically and olfactory pleasing to the
consumer. In particular, the products also need to meet certain
physical parameters in order to ensure that the product can be
easily applied to the hair by the consumer to provide the desired
effect, without unintentional staining of the consumers' clothes,
skin or other objects.
The manufacturer is also required to provide the hair colouring
consumer a large range of different resulting colours. Some
consumers may just wish to enhance the natural colour of the hair,
whilst others may wish to cover grey or completely alter the hair
colour to a different natural appearing hair colour or a
`synthetic` appearing hair colour. Consequently, the manufacturer
may provide over twenty different formulations, of varying colours
and shades, to address the range of consumer specific needs. These
formulations have to be individually formulated and are typically
complex formulae containing a mixture of different dye compounds.
As a result the manufacture of such product ranges can be costly
and complex.
However, despite the fact that commercial hair dyeing products have
been available for many years, the products still exhibit a number
of consumer-related deficiencies.
Typically permanent hair dye products will contain an alkali,
typically a source of ammonia. This serves the purpose of swelling
the hair allowing the entry of the dye precursor molecules into the
hair and also improves the lightening effect of the oxidising
agent, which is typically hydrogen peroxide. However, ammonia is
also volatile and its associated odour is extremely unpleasant to
the consumers' of such products, particularly as these hair dye
products are used in close proximity to the nasal region. Hence, it
would be highly desirable to provide an oxidative hair colouring
and/or bleaching composition, which delivers the consumer required
lightening level and colour but which has reduced or eliminated the
detectable ammonia odour.
In fact another deficiency area in current hair colouring products
is the provision of hair colouring products which deliver the
required hair lightening effect. Delivering the required level of
lightening is particularly important in order to provide the full
range of colour shades demanded by the consumer, especially for
blonde shades and grey coverage. Such products pose particular
difficulties to the manufacturer, as they usually require the use
of high levels of oxidising agent and ammonia in order to deliver
the required lightening effect. However, in additional to the
problems associated with the presence of high levels of ammonia in
these products, as discussed herein above, the presence of these
high levels of ammonia and/or oxidizing agent also affect the
condition of the hair and may in some cases induce mild skin
irritation on the scalp. In particular, the hydrophilicity of the
hair surface is increased during the colouring process, which
alters the sensory perception of the hair and its overall
manageability during, immediately after colouring and during the
subsequent wash and styling cycles until the next colourant
application. Hence, it would also be highly desirable to provide an
oxidative hair colouring and/or bleaching composition which
delivers the required lightening and/or colour without unnecessary
hair damage.
A number of attempts have been described in the literature to
address at least some of the above identified improvement areas.
For example the use of carbonate has been described in the
following hair colouring art.
EP 435 012 describes hair-dyeing compositions, which require a
short dyeing time, create little damage to hair, and no irritating
odour after dyeing comprising a carbonate source, a non odour
generating alkali hydrogen peroxide and a buffer solution.
Similarly EP 1 106 166 describes hair dye compositions comprising
ammonia, carbonate (other than ammonia salt), transition metal salt
and chelating agent which do not give off an irritating odour, have
low skin irritation and can change the hair colour into a lighter
tone in a short time. WO01/28508 describes hair colouring
formulations comprising oxidising agents and ammonia carbonate or
carbamate which deliver improved bleaching and colouring with
reduced odour and hair damage without the need for buffering
agents, pH modifiers or hair swelling agents. JP01206825 describes
a low pungent hair colouring composition comprising ammonia,
ammonium salt and carbonate. The composition may also comprise
alkanolamine to improve resistance to decolouration.
JP11343219 discloses hair bleaching compositions comprising
ammonia, or ammonium ion and carbonate ion. Similarly DE 296 13 065
U1 discloses a hair beaching powder comprising hydrogen peroxide,
ammonium salt and alkali carbonate or alkali hydrogen
carbonate.
However it has now been found that a problem related to the use of
hydrogen peroxide and carbonate hair colourant systems is that,
particularly in the presence of high levels of peroxide and
carbonate, the hair colourant compositions can under certain
conditions result in significant damage to the hair fibres.
Consequently, the hair fibres are substantially weakened and may
become so brittle that breakage occurs during the consumers' normal
hair maintenance routine.
Another particularly critical performance area for the consumer is
the provision of the desired resultant colour and also the
effective coverage of grey hair. Indeed, whilst the amount of grey
hair to be coloured varies considerably from consumer to consumer,
the resultant overall appearance of the coloured hair demanded by
the consumer should be nearly identical for the naturally pigmented
hair and the grey hair on head, with the added requirement that the
initial coverage is maintained during the post dyeing washing and
drying cycle.
Hence, it would be further desirable to provide the consumer with a
hair colourant, providing improved lift and lightening, reduced
damage, particularly brittle fibre formation, and improved colour
delivery, uptake and durability.
It has now been surprisingly found that oxidative hair colouring
compositions comprising an oxidising agent, a source of carbonate
ions, an alkalising agent, preferably a source of ammonia and a
specific radical scavenger as defined herein below utilised at a pH
9.5 and below provide a low odour colouring composition which
delivers a high level of lift and lightening equal to the currently
utilised ammonia/peroxide systems, whilst reducing the
concentration of peroxide and reducing the hair fibre damage.
Moreover, the compositions of the present invention are compatible
with current dyes and dye precursor systems and result in improved
lift and lightening for blond shades, excellent dye deposition and
colour and improved grey coverage.
A number of documents in the literature describe a large number of
a wide variety of compounds, which may be considered to have
radical scavenging activity for use in beauty care products. For
example EP840593A describes an oxidative hair colourant comprising
developers and optionally couplers, having a pH of 8 to 11 and an
alkalising agent comprising a mixture of amino acids and
oligopeptides and certain alkanolamine derivatives to reduce
ammonia odour and reduce hair damage. U.S. Pat. No. 3,899,288
describes keratinous fibre oxidative dyeing compositions comprising
oxidative dye precursors, and a carbonate alkali metal salt of an
amino acid for reducing ammonia odour. Similarly, DE2215303
discloses hair dyeing compositions comprising guanidine compounds,
arginine protamine or polypepetides oxidative dye precursors and
peroxide, to provide odour free compositions and which do not cause
skin irritation. U.S. Pat. No. 3,997,659 describes hair bleaching
compositions containing arginine or various proteins or peptides
having a high arginine content, peroxide and a bleaching
accelerator to reduce odour and reduce hair damage.
However, none of these documents describe the features and benefits
of the presently claimed invention.
SUMMARY OF THE INVENTION
The present invention relates to a hair colouring and hair
bleaching composition comprising i) at least one source of
peroxymonocarbonate ions, ii) at least one source of alkalizing
agent, preferably ammonium ions and iii) at least one source of
radical scavenger, wherein said composition has a pH of up to and
including 9.5.
In another embodiment the present invention relates to a hair
colouring and bleaching kits comprising an individually packaged
component comprising at least one source of radical scavenger.
In yet another embodiment the present invention also relates to
hair colouring and bleaching kits comprising an individually
packaged oxidizing component comprising at least one source of
peroxymonocarbonate ion, preferably a source of hydrogen peroxide
and an individually packaged colouring component comprising at
least one source of radical scavenger, at least one source of
carbonate ions, carbamate ions and or hydrocarbonate ions and at
least one alkalizing agent.
The present invention also relates to a method of treating hair
comprising the steps of applying a composition comprising at least
one source of peroxymonocarbonate ions, at least one alkalizing
agent and at least one source of radical scavenger, wherein said
composition has a pH of up to 9.5 for at least 50% of the time
period said composition is applied and retained on the hair.
The present invention also relates to a method of treating hair
comprising the steps of i) applying a composition comprising at
least one source of radical scavenger and ii) separately applying
an oxidizing hair colouring composition comprising at least one
source of peroxymonocarbonate ion and at least one source of
alkalizing agent wherein said steps i) and ii) are
interchangeable
In a further aspect the present invention relates to the use of the
claimed to reduce the damage to hair fibres and reduce the odour of
the compositions.
DETAILED DESCRIPTION OF THE INVENTION
While the specification concludes with claims, which particularly
point out and distinctly claim the invention, it is believed the
present invention will be better understood from the following
description.
As used herein the term "hair" to be treated may be "living" i.e.
on a living body or may be "non-living" i.e. in a wig, hairpiece or
other aggregation of non-living keratinous fibers. Mammalian,
preferably human hair is preferred. However wool, fur and other
keratin containing fibers are suitable substrates for the
compositions according to the present invention.
All percentages are by weight of the total composition unless
specifically stated otherwise. When more than one composition are
used during a treatment, the total weight to be considered is the
total weight of all the compositions applied on the hair
simultaneously (i.e. the weight found "on head") unless otherwise
specified. All ratios are weight ratios unless specifically stated
otherwise.
Currently marketed hair permanent colourant products typically
utilize a combination of an alkaliser system, dye precursors and an
oxidant to deliver the desired hair colour to the consumer. The
alkaliser is typically ammonia or an alkanolamine, such as
monoethanolamine and the oxidant is typically hydrogen peroxide or
a solid form of hydrogen peroxide. The final hair colour which is
delivered to the consumer is a combination of the result of the
underlying bleaching of the melanin pigment in the hair fibre and
the delivery of the coloured dye chromophore moities which are
either preformed, that is direct dyes or are formed by
oxidatization of the dye precursors within the hair fibre.
The optimal pH for such systems is typically about pH 10.0. This
high pH is necessary in order to produce a sufficient concentration
of the perhydroxy anion (HOO--) to give the desired bleaching of
the melanin. It has been found that below pH 9.5 the concentration
of this species is less than 0.01% of the added hydrogen peroxide
concentration (pKa=11.6) and the amount of melanin bleaching drops
dramatically and is hence insufficient to give the desired final
colour.
However, as discussed herein above, compositions having a high pH
cause many of the disadvantages noted by consumers for these
colourant systems. In particular, the level of the volatile ammonia
increases at high pH (above pH 9.5) giving increased unpleasant
odour. Furthermore, reactive species including the perhydroxy anion
reacts with the hair fibre resulting in significant fibre damage.
One consequence of this reactivity is that the hydrophilicity of
the hair fibres is significantly increased and this causes an
increase in the force required to comb the hair compared with hair
that has not been coloured. Moreover the higher forces that are
exerted during combing and styling result in increased fibre damage
to the hair fibres.
It has now been surprisingly found that hair colouring and
bleaching compositions comprising the combination of at least one
source of peroxymonocarbonate ions, preferably formed insitu from a
source of hydrogen peroxide and a carbonate ion source, at least
one source of alkalizing agents, at least one source of radical
scavenger, (as defined hereinafter), and preferably dyes and/or dye
precursors, can deliver the same or improvements of the desired
hair colour results, but at a pH of below 9.5, preferably from 7.5
to 9.5, hence considerably reducing the odour and the damage to the
hair fibres.
Whilst not wishing to be bound by theory, it is believed that in
the present invention the key species responsible for the bleaching
of the melanin, namely the peroxymonocarbonate ion (--OC(O)OOH),
decomposes at pH values above 9.5 to form oxygen and the hydrogen
carbonate ion. At pH values below 7.5 the hydrogen carbonate ion
decomposes to form carbon dioxide and water. At pH values of 9.0
the bleaching of the melanin and the final colour observed is at an
optimal level. Thus surprisingly the present invention allows for
the delivery of improved lift, that is hair lightening which is a
highly desirable consumer need. Furthermore, compositions having a
pH lower than 9.5 have the benefit that not only the unpleasant
ammonia odour is significantly reduced but also the hair fibre
damage is reduced. These benefits are shown in the table 1
hereinafter.
A further aspect of the present invention concerns the utilization
of radical scavenger species. It has now been surprisingly found
that the addition of a radical scavenger compound as defined herein
maintains the internal hair fibre strength as shown in the tensile
strength data, hereinafter table (2). In this table (2) the loss of
internal strength relative to the hair before colouring is shown
(the force to 15% extension and the force to break the fibres).
Whilst not wishing to be bound by theory, it is believed that this
effect relates to the fact that an undesired side reaction of the
hair coloring process can take place in the hair when hair
colourant compositions comprising hydrogen peroxide and ammonium
carbonate are utilized. This side reaction is the formation of
carbonate radicals either on the hair fibre surface or in the hair
fibre itself. These carbonate radicals can react with the keratin
leading to a dramatic decrease in the internal strength of the hair
fibre. This loss of internal strength can clearly be seen in the
loss of tensile strength verses the untreated hair in both its
force to 15% extension and the force required to break the fibre
(see table 2). Surprisingly, the addition of a radical scavenger to
the hair dye composition effectively removes and/or deactivates
these harmful carbonate radicals and rapidly transforms them to
relatively harmless species. For optimum efficacy the radical
scavenger should preferably have the appropriate reactivity profile
to react with the carbonate radical and should preferably be able
to rapidly penetrate through the hair fibre.
Oxidizing Agent
The compositions according to the present invention thus comprise a
source of peroxymonocarbonate ions. These ions are typically formed
insitu from the reaction between a source of hydrogen peroxide and
carbonate ion. Consequently, the compositions according to the
present invention comprise or are used in combination with a
composition that comprises at least one source of an oxidizing
agent. Preferred oxidizing agents for use herein are water-soluble
peroxygen oxidizing agents. "Water-soluble" as defined herein means
that in standard condition at least 0.1 g, preferably 1 g, more
preferably 10 g of said oxidizing agent can be dissolved in 1 liter
of deionized water. The oxidizing agents are valuable for the
initial solubilisation and decolorisation of the melanin
(bleaching) and accelerate the oxidation of the oxidative dye
precursors (oxidative dyeing) in the hair shaft.
Any oxidizing agent known in the art may be utilized in the present
invention. Preferred water-soluble oxidizing agents are inorganic
peroxygen materials capable of yielding hydrogen peroxide in an
aqueous solution. Water-soluble peroxygen oxidizing agents are well
known in the art and include hydrogen peroxide, inorganic alkali
metal peroxides such as sodium periodate and sodium peroxide and
organic peroxides such as urea peroxide, melamine peroxide, and
inorganic perhydrate salt bleaching compounds, such as the alkali
metal salts of perborates, percarbonates, perphosphates,
persilicates, persulphates and the like. These inorganic perhydrate
salts may be incorporated as monohydrates, tetrahydrates etc. Alkyl
and aryl peroxides and or peroxidases may also be used. Mixtures of
two or more such oxidizing agents can be used if desired. The
oxidizing agents may be provided in aqueous solution or as a powder
which is dissolved prior to use. Preferred for use in the
compositions according to the present invention are hydrogen
peroxide, percarbonate (which may be used to provide a source of
both oxidizing agent and carbonate ions), persulphates and
combinations thereof.
According to the present invention the compositions comprise from
about 0.1% to about 10% by weight, preferably from about 1% to
about 7% by weight, and most preferably from about 2% to about 5%
by weight of an oxidizing agent.
Carbonate Ion Source
According to the present invention the compositions thus also
comprise at least a source of carbonate ions or carbamate ions or
hydrocarbonate ions or any mixture thereof. Any source of these
ions may be utilized. Suitable sources for use herein include
sodium, potassium, guanidine, arginine, lithium, calcium,
magnesium, barium, ammonium salts of carbonate, carbamate and
hydrocarbonate ions and mixtures thereof such as sodium carbonate,
sodium hydrogen carbonate, potassium carbonate, potassium hydrogen
carbonate, guanidine carbonate, guanidine hydrogen carbonate,
lithium carbonate, calcium carbonate, magnesium carbonate, barium
carbonate, ammonium carbonate, ammonium hydrogen carbonate and
mixtures thereof. Percarbonate salts may also be utilized to
provide both the source of carbonate ions and oxidizing agent.
Preferred sources of carbonate ions, carbamate and hydrocarbonate
ions are sodium hydrogen carbonate, potassium hydrogen carbonate,
ammonium carbamate and mixtures thereof.
The compositions of the present invention may comprise from about
0.1% to about 15%, preferably from about 0.1% to about 10% by
weight, more preferably from about 1% to about 8% by weight of the
carbonate ion. Preferably, if present, the ammonium ions and
carbonate ions are present in the composition at a weight ratio of
from about 3:1 to 1:10, preferably about 2:1 to 1:5. In a
particularly preferred embodiment of the present invention the
ammonium ions and carbonate ion sources are provided by a single
source such as ammonium carbonate, ammonium hydrogen carbonate,
ammonium hydrocarbonate or mixtures thereof.
Source of Alkalizing Agent
According to the present invention the composition also comprises
at least one source of alkalizing agent, preferably a source of
ammonium ions and or ammonia. Any agent known in the art may be
used such as alkanolamides for example monoethanolamine,
diethanolamine, triethanolamine, monopropanolamine,
dipropanolamine, tripropanolamine,
2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and
2-amino-2-hydroxymethyl-1,3-propanediol and guanidium salts.
Particularly, preferred alkalizing agents are those which provide a
source of ammonium ions. Any source of ammonium ions is suitable
for use herein. Preferred sources include ammonium chloride,
ammonium sulphate, ammonium nitrate, ammonium phosphate, ammonium
acetate, ammonium carbonate, ammonium hydrogen carbonate, ammonium
carbamate, ammonium hydroxide, percarbonate salts, ammonia and
mixtures thereof. Particularly preferred are ammonium carbonate,
ammonium carbamate, ammonia and mixtures thereof
The compositions of the present invention may comprise from about
0.1% to about 10% by weight, preferably from about 0.5% to about
5%, most preferably from about 1% to about 3% of an alkalizing
agent, preferably ammonium ions.
Radical Scavenger
According to the present invention the compositions further
comprise a source of radical scavenger. As used herein the term
radical scavenger refers to a species that can react with a
carbonate radical to convert the carbonate radical by a series of
fast reactions to a less reactive species, i.e. a carbonate radical
scavenger.
Whilst not being bound by theory, it is believed that the ability
of the radical scavenger to convert the carbonate radical (as
described hereinabove) is dependant upon the energy of the charge
transfer reaction as shown below: (The calculation of the energy of
the charge transfer reaction is detailed hereinafter.)
Scavenger+CO.sub.3.sup.*-.fwdarw.Scavenger.sup.*+CO.sub.3.sup.2-
wherein the energy of the reaction is defined by:
.DELTA..times..times..DELTA..times..times..function..DELTA..times..times.-
.function..times..times..DELTA..times..times..function..DELTA..times..time-
s..function..times..DELTA..times..times..function..DELTA..times..times..fu-
nction. ##EQU00001##
According to the present invention radical scavengers suitable for
use herein have an energy of reaction of from about 0 kcal/mol to
about 14 kcal/mol, preferably from about 1.5 kcal/mol to about 9
kcal/mol.
Suitable radical scavengers for use herein include compounds
according to the general formula:
R.sup.1--Y--C(H)(R.sup.3)--R.sup.4--(C(H)(R.sup.5)--Y--R.sup.6).sub.n
(I):
wherein Y is NR.sup.2, O, or S, preferably NR.sup.2, n is 0 to 2,
and wherein R.sup.4 is monovalent or divalent and is selected from:
(a) substituted or unsubstituted, straight or branched, alkyl,
mono-or poly-unsaturated alkyl, heteroalkyl, aliphatic,
heteroaliphatic, or heteroolefinic systems, (b) substituted or
unsubstituted, mono- or poly-cyclic aliphatic, aryl, or
heterocyclic systems, or (c) substituted or unsubstituted, mono-,
poly-, or per-fluoro alkyl systems; the systems of (a), (b) and (c)
comprising from 1 to 12 carbon atoms and 0 to 5 heteroatoms
selected from O, S, N, P, and Si; and wherein R.sup.4 can be
connected to R.sup.3 or R.sup.5 to create a 5, 6 or 7 membered
ring; and wherein R.sup.1, R.sup.2, R.sup.3, R.sup.5, and R.sup.6
are monovalent and are selected independently from: (a), (b) and
(c) described herein above, or H.
Preferably, R.sup.4 is selected from: (a) substituted or
unsubstituted, straight or branched, alkyl, heteroalkyl, aliphatic,
heteroaliphatic, or heteroolefinic systems, (b) substituted or
unsubstituted, mono- or poly-cyclic aliphatic, aryl, or
heterocyclic systems, or (c) substituted or unsubstituted, mono-,
poly-, or per-fluoro alkyl systems; more preferably R.sup.4 is
selected from (a) substituted or unsubstituted, straight or
branched, alkyl, heteroalkyl, aliphatic, or heteroaliphatic
systems, (b) substituted or unsubstituted, aryl, or heterocyclic
systems, or (c) substituted or unsubstituted, mono-, poly-, or
per-fluoro alkyl systems; more preferably substituted or
unsubstituted, straight or branched, alkyl, or heteroalkyl
systems.
Preferably, the R.sup.4 systems of (a), (b), and (c), described
herein above, comprise from 1 to 8 carbon atoms, preferably from 1
to 6, more preferably from 1 to 4 carbon atoms and from 0 to 3
heteroatoms; preferably from 0 to 2 heteroatoms; most preferably
from 0 to 1 heteroatoms. Where the systems contain heteroatoms,
preferably they contain 1 heteroatom. Preferred heteroatoms include
O, S, and N; more preferred are O, and N; and most preferred is
O.
Preferably, R.sup.1, R.sup.2, R.sup.3, R.sup.5, and R.sup.6 are
selected independently from any of the systems defined for R.sup.4
above, and H.
In alternative embodiments, any of R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 groups are substituted. Preferably,
the substituent(s) is selected from: (a) the group of C-linked
monovalent substituents consisting of: (i) substituted or
unsubstituted, straight or branched, alkyl, mono- or
poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or
heteroolefinic systems, (ii) substituted or unsubstituted, mono- or
poly-cyclic aliphatic, aryl, or heterocyclic systems, or (iii)
substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl
systems; said systems of (i), (ii) and (iii) comprising from 1 to
10 carbon atoms and 0 to 5 heteroatoms selected from O, S, N, P,
and Si; (b) the group of S-linked monovalent substituents
consisting of SA.sup.1, SCN, SO.sub.2A.sup.1, SO.sub.3A.sup.1,
SSA.sup.1, SOA.sup.1, SO.sub.2NA.sup.1A.sup.2, SNA.sup.1A.sup.2,
and SONA.sup.1A.sup.2; (c) the group of O-linked monovalent
substituents consisting of OA.sup.1, OCN and ONA.sup.1A.sup.2; (d)
the group of N-linked monovalent substituents consisting of
NA.sup.1A.sup.2, (NA.sup.1A.sup.2A.sup.3).sup.+, NC,
NA.sup.1OA.sup.2, NA.sup.1SA.sup.2, NCO, NCS, NO.sub.2,
N.dbd.NA.sup.1, N.dbd.NOA.sup.1, NA.sup.1CN,
NA.sup.1NA.sup.2A.sup.3; (e) the group of monovalent substituents
consisting of COOA.sup.1, CON.sub.3, CONA.sup.1.sub.2,
CONA.sup.1COA.sup.2, C(.dbd.NA.sup.1)NA.sup.1A.sup.2, CHO, CHS, CN,
NC, and X; and (f) the group consisting fluoroalkyl monovalent
substituents consisting of mono-, poly-, or per-fluoro alkyl
systems comprising from 1 to 12 carbon atoms and 0 to 4
heteroatoms.
For the groups (b) to (e), described above, A.sup.1, A.sup.2, and
A.sup.3 are monovalent and are independently selected from: (1) H,
(2) substituted or unsubstituted, straight or branched, alkyl,
mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,
heteroaliphatic, or heteroolefinic systems, (3) substituted or
unsubstituted, mono- or poly-cyclic aliphatic, aryl, or
heterocyclic systems, or (4) substituted or unsubstituted, mono-,
poly-, or per-fluoro alkyl systems; said systems of (2), (3) and
(4) comprising from 1 to 10 carbon atoms and 0 to 5 heteroatoms
selected from O, S, N, P, and Si; and wherein X is a halogen
selected from the group consisting of F, Cl, Br, and I.
Preferred substituents for use herein include those having a
Hammett Sigma Para (.sigma..sub.p) Value from -0.65 to +0.75,
preferably from -0.4 to +0.5. Hammett Sigma Values are described in
Advanced Organic Chemistry--Reactions, Mechanisms and Structure
(Jerry Mar. 5.sup.th ed. (2001) at pages 368 375). Without being
limited by theory, it is believed that substituents having sigma
para values in the chosen ranges, when substituted onto R.sup.1
and/or R.sup.2, may improve the compound's toxicological profile
without unduly adding an unfavourable increase in molecular weight
that may interfere with the molecule's ability to penetrate the
hair shaft. Some preferred substituents and their Hammett Sigma
Para values are shown below, in Table A. Additional substituents
and their values are shown in March, at page 370.
TABLE-US-00001 TABLE A Substituent NH.sub.2 OH H COO-- Cl COOH
CF.sub.3 .quadrature..sub.p -0.57 -0.38 0 0.11 0.24 0.44 0.53
Preferably the above defined radical scavengers have a pKa of more
than 7 to prevent the protonation of the nitrogen.
Alternative suitable radical scavengers for use herein are
compounds according to the general formula (II):
##STR00001## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and
R.sub.5 are each independently selected from H, COO.sup.-M.sup.+,
Cl, Br, SO.sub.3.sup.- M.sup.+, NO.sub.2, OCH.sub.3, OH or a
C.sup.1 to C.sup.10 primary or secondary alkyl and M is either H or
alkali metal. Preferably, the above-described radical scavengers
have a pKa of more than 8.5 to ensure protonation of the hydroxy
goup.
Other suitable radical scavengers for use herein include those
selected from the group consisting of benzylamine, imidazole,
di-tert-butylhydroxytoluene, hydroquinone, guanine, pyrazine,
piperidine, morpholine, methylmorpholine, 2-methyoxyethylamine, and
mixtures thereof.
Preferred radical scavengers according to the present invention are
selected from the classes of alkanolamines, amino sugars, amino
acids, esters of amino acids and mixtures thereof. Particularly
preferred compounds are: monoethanolamine, 3-amino-1-propanol,
4-amino-1-butanol,5-amino-1-pentanol, 1-amino-2-propanol,
1-amino-2-butanol, 1-amino-2-pentanol, 1-amino-3-pentanol,
1-amino-4-pentanol, 3-amino-2-methylpropan-1-ol,
1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, glucosamine,
N-acetylglucosamine, glycine, arginine, lysine, proline, glutamine,
histidine, sarcosine, serine, glutamic acid, tryptophan, and
mixtures thereof, and the salts such as the potassium, sodium and
ammonium salts thereof and mixtures thereof.
Especially preferred compounds are glycine, sarcosine, lysine,
serine, 2 methoxyethylamine, glucosamine, glutamic acid,
morpholine, piperdine, ethylamine, 3 amino-1-propanol and mixtures
thereof.
The radical scavengers according to the present invention
preferably have a molecular weight of less than about 500,
preferably less than about 300, more preferably less than about 250
in order to facilitate penetration of the radical scavenger into
the hair fibre.
The compositions of the present invention preferably comprise from
about 0.1% to about 10% by weight, preferably from about 1% to
about 7% by weight of radical scavenger. Preferably, the radical
scavenger is present at an amount such that the weight ratio of
radical scavenger to carbonate ion is from about 2:1 to about 1:4.
The radical scavenger is also preferably selected such that it is
not an identical species as the alkalizing agent. According to one
embodiment of the present invention the radical scavenger may be
formed insitu in the hair dyeing compositions prior to application
to the hair fibres.
pH
The compositions of the present invention have a pH up to and
including pH 9.5. Preferably, the compositions of the present
invention have a pH of from about 9.5 to about 7.5, more preferably
from about 9.5 to about 8.4 and most preferably from about 9.4 to
about 8.5 and even more preferably about pH 9.0.
Preferably the compositions of the present invention are prepared
such that prior to application to the hair fibres the pH of the
composition is no greater than about pH 9.5. However, in another
embodiment of the present invention the compositions may be
formulated such that the pH is up to 9.5 during the time period of
application of the composition to the hair fibres prior to removal
therefrom. Preferably, the pH is up to about 9.5 for at least about
50% of the time period, preferably at least about 70%, most
preferably at least about 80% of the time period of application of
the composition to the hair. More preferably, the pH of the
composition is up to about pH 9.5 within about 10 minutes,
preferably within about 5 minutes of application to the hair
fibres.
The pH of the compositions can be determined by using either a
Mettler Toledo MP220 or a MP225 pH equipment, fitted with a
standard laboratory pH electrode. The equipment is calibrated
before each use using standard calibration buffers and using
standard calibration procedure.
It is known that for good lightening and good colour formation that
the final formulation should have a good buffering capacity or
reserve alkalinity (the ability of the system to resist the pH
shift that would otherwise be caused by addition of acid). The
reserve alkalinity is measured by titration with o.1N methaolic
hydrochloric acid being added to 0.7 mL of thoroughly mixed
colouring composition in 50 mL of methanol. The sharpest end point
of the titration is measured by a pH electrode. It has been
determined that a reserve alkalinity of at least 0.2
milli-equivalents of titratable alkalinity per gram of mixed
colouring composition and preferably above 0.4 is required for good
lightening and colouring. Suitable buffering systems include
ammonia/ammonium acetate mixtures, monoethanolamine tetrasodium
pyrophosphate, isopropanolamine, benzoic acid.
Additional Components
The compositions of the present invention may further comprise
additional ingredients which include, but are not limited to, hair
dyeing agents such as oxidative dye precursors, non-oxidative dyes,
thickeners, solvents, enzymes, surfactants, conditioning agents,
carriers, antioxidants, stabilizers, chelants, perming actives,
perfume, reducing agents (thiolactic acid), hair swelling agents
and/or polymers. Some of these additional components are detailed
hereafter.
Hair Dyes
The hair colouring compositions of the present invention are
preferably hair colouring compositions which comprise oxidative
dyeing compositions. Such compositions comprise oxidative hair dye
precursors (also known as primary intermediates) that will deliver
a variety of hair colors to the hair. These small molecules are
activated by the oxidizing agent and react with further molecules
to form a larger colored complex in the hair shaft.
The precursors can be used alone or in combination with other
precursors, and one or more can be used in combination with one or
more couplers. Couplers (also known as color modifiers or secondary
intermediates) are generally colorless molecules that can form
colors in the presence of activated precursors, and are used with
other precursors or couplers to generate specific color effects or
to stabilize the color.
The choice of precursors and couplers will be determined by the
color, shade and intensity of coloration that is desired. The
precursors and couplers can be used herein, singly or in
combination, to provide dyes having a variety of shades ranging
from ash blonde to black.
These compounds are well known in the art, and include aromatic
diamines, aminophenols, and their derivatives (a representative but
not exhaustive list of oxidation dye precursor can be found in
Sagarin, "Cosmetic Science and Technology", Interscience, Special
Edn. Vol. 2 pages 308 to 310). It is to be understood that the
precursors detailed below are only by way of example and are not
intended to limit the compositions and processes herein. These
are:
p-phenylenediamine derivatives, e.g. benzene-1,4diamine (commonly
known as p-phenylenediamine), 2-methyl-benzene-1,4-diamine,
2-chloro-benzene-1,4-diamine, N-phenyl-benzene-1,4-diamine,
N-(2-ethoxyethyl)benzene-1,4-diamine,
2-[(4-amino-phenyl)-(2-hydroxyethyl)-amino]-ethanol, (commonly
known as N,N-bis(2-hydroxyethyl)-p-phenylenediamine)
(2,5-diamino-phenyl)-methanol,
1-(2'-Hydroxyethyl)-2,5-diaminobenzene,
2-(2,5-diamino-phenyl)-ethanol,
N-(4-aminophenyl)benzene-1,4-diamine,
2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine,
1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine,
1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol,
N.sup.4,N.sup.4,2-trimethylbenzene-1,4-diamine,
2-methoxy-benzene-1,4-diamine,
1-(2,5-diaminophenyl)ethane-1,2-diol,
2,3-dimethyl-benzene-1,4-diamine,
N-(4-amino-3-hydroxy-phenyl)-acetamide,
2,6-diethylbenzene-1,4-diamine, 2,5-dimethylbenzene-1,4-diamine,
2-thien-2-ylbenzene-1,4-diamine, 2-thien-3-ylbenzene-1,4-diamine,
2-pyridin-3-ylbenzene-1,4-diamine, 1,1'-biphenyl-2,5-diamine,
2-(methoxymethyl)benzene-1,4-diamine,
2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol,
N-[2-(2,5-diaminophenoxy)ethyl]-acetamide,
N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine,
N,N-dipropylbenzene-1,4-diamine,
2-[(4-aminophenyl)(ethyl)amino]ethanol,
2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,
N-(2-methoxyethyl)-benzene-1,4-diamine,
3-[(4-aminophenyl)amino]propan-1-ol,
3-[(4-aminophenyl)-amino]propane-1,2-diol,
N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine, and
2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-1,3--
Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;
2,2'-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine-
; N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; p-aminophenol
derivatives such as: 4-amino-phenol (commonly known as
p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyl-phenol,
4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol,
4-amino-1-hydroxy-2-(2'-hydroxyethylaminomethyl)benzene,
4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid,
1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol,
4-amino-2-(2-hydroxy-ethyl)-phenol,
4-amino-3-(hydroxymethyl)phenol, 4-amino-3-fluoro-phenol,
4-amino-2-(aminomethyl)-phenol, 4-amino-2-fluoro-phenol;
1-Hydroxy-2,4-diaminobenzene;
1-(2'-Hydroxyethyloxy)-2,4-diaminobenzene;
2,4-Diamino-5-methylphenetol; o-phenylenediamine derivatives such
as: 3,4-Diaminobenzoic acid and salts thereof; o-aminophenol
derivatives such as: 2-amino-phenol (commonly known as
o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol,
2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide,
and 2-amino-4-methyl-phenol; and heterocyclic derivatives such as:
pyrimidine-2,4,5,6-tetramine (commonly known as
2,4,5,6-tetraaminopyridine), 1-methyl-1H-pyrazole-4,5-diamine,
2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,
N.sup.2,N.sup.2-dimethyl-pyridine-2,5-diamine,
2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol,
6-methoxy-N.sup.2-methyl-pyridine-2,3-diamine,
2,5,6-triaminopyrimidin4(1H)-one, pyridine-2,5-diamine,
1-isopropyl-1H-pyrazole-4,5-diamine,
1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,
1-(benzyl)-1H-pyrazole4,5-diamine,
1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine,
pyrazolo[1,5-a]-pyrimidine-3,7-diamine,
5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,
7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,
2,5,6,7-teramethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride, 5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride,
5,7-di-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride, 2-methylpyrazolo[1,5-a]pyrimidin-3,7-diamine
hydrochloride; 4-Hydroxy-2,5,6-triaminopyrimidine;
1-(2'hydroxyethyl)-amino-3,4-methylene dioxybenzene; and
1-Hydroxyethyl-4,5-diaminopyrazole sulphate.
Additional developers include N-(3-furylmethyl)benzene-1,4-diamine;
N-Thiophen-3-ylmethyl-benzene-1,4-diamine;
N-(2-furylmethyl)benzene-1,4-diamine;
N-Thiophen-2-ylmethyl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid
(2,5-diamino-benzylidene)-hydrazide;
3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;
2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;
2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;
2-(6-Methyl-pyridin-2-yl)-benzene-1,4-diamine;
2-Pyridin-2-yl-benzene-1,4-diamine;
2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;
2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;
3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;
2-Thiazol-2-yl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid
(2,5-diamino-benzylidene)-hydrazide;
3'-Fluoro-biphenyl-2,5-diamine; 2-Propenyl-benzene-1,4-diamine;
2'-Chloro-biphenyl-2,5-diamine;
N-Thiophen-3-ylmethyl-benzene-1,4-diamine;
N-(3-furylmethyl)benzene-1,4-diamine;
4'-Methoxy-biphenyl-2,5-diamine;
N-(4-Amino-benzyl)-benzene-1,4-diamine;
2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;
5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;
5-Isopropylamino-2-methyl-phenol; Biphenyl-2,4,4'-triamine
hydrochloride; 5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine
hydrochloride; 5-Phenylaminomethyl-benzene-1,3-diamine
hydrochloride;
2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol
hydrochloride; 5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine
hydrochloride; N-(2-Amino-benzyl)-benzene-1,3-diamine
hydrochloride; N-Furan-2-ylmethyl-benzene-1,3-diamine
hydrochloride; 2-[(3-Amino-phenylamino)-methyl]-phenol
hydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride;
N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;
N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phen-
yl)-acrylamide; hydrochloride;
4-Amino-2-(isopropylamino-methyl)-phenol; hydrochloride;
4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride hydrochloride;
5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;
5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;
4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride;
2',4'-Diamino-biphenyl-4-ol; hydrochloride;
5-Cyclobutylamino-2-methyl-phenol;
5-Cyclobutylamino-2-methyl-phenol;
4-Amino-2-(pyridin-3-ylaminomethyl)-phenol;
5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;
5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;
N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;
N-Benzyl-benzene-1,3-diamine hydrochloride;
3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;
N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;
N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;
4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol;
hydrochloride; 2',4'-Diamino-biphenyl-4-ol hydrochloride;
Biphenyl-2,4,4'-triamine; 5-(4-Amino-phenyl)
aminomethyl-benzene-1,3-diamine hydrochloride;
2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol
hydrochloride; 5-Allylaminomethyl-benzene-1,3-diamine
hydrochloride; 5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine
hydrochloride; N-(4-Amino-benzyl)-benzene-1,3-diamine
hydrochloride; N-Benzyl-benzene-1,3-diamine hydrochloride;
3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;
N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;
N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;
N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;
2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;
N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;
N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;
N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phen-
yl)-acrylamide hydrochloride; 4-Amino-2-propylaminomethyl-phenol;
hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol
hydrochloride;
4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol
hydrochloride; 2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;
5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;
5-Isopropylamino-2-methyl-phenol;
5-Cyclobutylamino-2-methyl-phenol;
4-Amino-2-(pyridin-3-ylarninomethyl)-phenol; and
5-Cyclobutylamino-2-methyl-phenol.
Preferred developers include: p-phenylenediamine derivatives such
as: 2-methyl-benzene-1,4-diamine; benzene-1,4-diamine;
1-(2,5-diamino-phenyl)-ethanol; 2-(2,5-diamino-phenyl)-ethanol;
N-(2-methoxyethyl)benzene-1,4-diamine;
2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;
1-(2,5-diaminophenyl)ethane-1,2-diol;
1-(2'-Hydroxyethyl)-2,5-diaminobenzene;
1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;
2,2'-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine-
; N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; and mixtures thereof;
p-aminophenol derivatives such as: 4-amino-phenol,
4-methylamino-phenol, 4-amino-3-methyl-phenol,
4-amino-2-methoxymethyl-phenol;
1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;
1-Hydroxy-2,4-diaminobenzene;
1-(2'-Hydroxyethyloxy)-2,4-diaminobenzene;
4-Amino-2-aminomethylphenol; 2,4-Diamino-5-methylphenetol;
4-Amino-1-hydroxy-2-(2'-hydroxyethylaminomethyl)benzene;
1-methoxy-2-amino-4-(2'hydroxyethylamino)-benzene; 5-aminosalicylic
acid and salts thereof; and mixtures thereof; o-phenylenediamine
derivatives such as: 3,4-Diaminobenzoic acid and salts thereof;
o-aminophenol derivatives such as: 2-amino-phenol,
2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,
N-(4-amino-3-hydroxy-phenyl)-acetamide; 2-amino-4-methyl-phenol;
and mixtures thereof; and heterocyclic derivatives such as:
pyrimidine-2,4,5,6-tetramine; 1-methyl-1H-pyrazole-4,5-diamine;
2-(4,5-diamino-1H-pyrazol-1-yl)ethanol;
1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine;
1-(benzyl)-1H-pyrazole-4,5-diamine;
N.sup.2,N.sup.2-dimethyl-pyridine-2,5-diamine;
4-Hydroxy-2,5,6-triaminopyrimidine;
1-(2'hydroxyethyl)-amino-3,4-methylene dioxybenzene; and
1-Hydroxyethyl-4,5-diaminopyrazole sulphate; and mixtures
thereof.
More preferred developers include: 2-methyl-benzene-1,4-diamine;
benzene-1,4-diamine; N,N-Bis(2-hydroxyethyl)-p-phenylenediamine;
4-amino-phenol; 4-methylamino-phenol; 4-amino-3-methyl-phenol;
1-Hydroxy-2,4-diaminobenzene; 2-amino-phenol;
2-amino-5-methyl-phenol; 2-amino-6-methyl-phenol;
1-methyl-1H-pyrazole-4,5-diamine;
1-Hydroxyethyl-4,5-diaminopyrazole sulphate;
2-(4,5-diamino-1H-pyrazol-1-yl)ethanol; and mixtures thereof.
Suitable couplers for use in the compositions described herein
include, but are not limited to: phenols, resorcinol and naphthol
derivatives such as: naphthalene-1,7-diol, benzene-1,3-diol,
4-chlorobenzene-1,3-diol, naphthalen-1-ol,
2-methyl-naphthalen-1-ol, naphthalene-1,5-diol,
naphthalene-2,7-diol, benzene-1,4-diol, 2-methyl-benzene-1,3-diol,
7-amino-4-hydroxy-naphthalene-2-sulfonic acid,
2-isopropyl-5-methylphenol,
1,2,3,4-tetrahydro-naphthalene-1,5-diol, 2-chloro-benzene-1,3-diol,
4-hydroxy-naphthalene-1-sulfonic acid, benzene-1,2,3-triol,
naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-1,3-diol,
4,6-dichlorobenzene-1,3-diol, 2,3-dihydroxy-[1,4]naphthoquinone;
and 1-Acetoxy-2-methylnaphthalene; m-phenylenediamines such as:
2,4-diaminophenol, benzene-1,3-diamine,
2-(2,4-diamino-phenoxy)-ethanol,
2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,
2-mehyl-benzene-1,3-diamine,
2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol,
4-{3-[(2,4-diaminophenyl)oxy]-propoxy}benzene-1,3-diamine,
2-(2,4-diamino-phenyl)-ethanol,
2-(3-amino-4-methoxy-phenylamino)-ethanol,
4-(2-amino-ethoxy)-benzene-1,3-diamine,
(2,4-diamino-phenoxy)-acetic acid,
2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol,
4-ethoxy-6-methyl-benzene-1,3-diamine,
2-(2,4-diamino-5-methyl-phenoxy)-ethanol,
4,6-dimethoxy-benzene-1,3-diamine,
2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol,
3-(2,4-diamino-phenoxy)-propan-1-ol,
N-[3-(dimethylamino)phenyl]urea,
4-methoxy-6-methylbenzene-1,3-diamine,
4-fluoro-6-methylbenzene-1,3-diamine,
2-({3-[(2-hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol,
3-(2,4-diaminophenoxy)-propane-1,2-diol,
2-[2-amino-4-(methylamino)-phenoxy]ethanol,
2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,
2-[(3-aminophenyl)amino]ethanol,
2,4-Diamino-5-(2'-hydroxyethyloxy)toluene;
N,N-Dimethyl-3-ureidoaniline; N-(2-aminoethyl)benzene-1,3-diamine,
4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine,
1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and
2,4-dimethoxybenzene-1,3-diamine; m-aminophenols such as:
3-amino-phenol, 2-(3-hydroxy-4-methyl-phenylamino)-acetamide,
2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol,
5-(2-hydroxy-ethylamino)-2-methyl-phenol,
5-amino-2,4-dichloro-phenol, 3-amino-2-methyl-phenol,
3-amino-2-chloro-6-methyl-phenol,
5-amino-2-(2-hydroxy-ethoxy)-phenol,
2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol,
5-amino-4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol,
5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,
5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol,
3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol,
5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol,
3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol,
5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol,
5-[(3-hydroxy-propyl)amino]-2-methylphenol,
3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol,
3-[(2-hydroxyethyl)amino]-2-methylphenol;
1-Methyl-2-hydroxy-4-(2'-hydroxyethyl)amino-benzene;
1,3-Bis-(2,4-Diaminophenoxy)propane;
1-Hydroxy-2-methyl-5-amino-6-chlorobenzene; and heterocyclic
derivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,
4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,
6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol,
2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol,
2-(1,3benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol,
5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine,
1,3-benzodioxol-5-amine,
2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol,
1H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol,
1H-indole-5,6-diol, 1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,
6-bromo-1,3-benzodioxol-5-aminopyridin-3-ol, pyridine-2,6-diamine,
3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol,
5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol,
1H-indole-2,3-dione, indoline-5,6-diol,
3,5-dimethoxypyridine-2,6-diamine, 6-methoxypyridine-2,3-diamine;
3,4-dihydro-2H-1,4-benzoxazin-6-amine; 4-hydroxy-N-methylindole,
1H-5-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,
2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,
2,6-dimethyl[3,2-c]-1,2,4-triazole,
6-methylpyrazolo-[1,5-a]benzimidazole, 2,6-dihydroxypyridine,
2,6-dihydroxy-3,4-dimethylpyridine,
5-methylpyrazolo[5,1-e]-1,2,3-triazole,
5-methyl-6-chloropyrazolo[5,1-e]-1,2,3,-triazole,
5-phenylpyrazolo[5,1-e]-1,2,3-triazole and its addition salts,
1H-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole tosylate,
7,8-dicyano-4-methylimidazolo-[3,2-a]imidazole,
2,7-dimethylpyrazolo[1,5-a]pyrimidin-5-one,
2,5-dimethylpyrazolo[1,5-a]pyrimidin-7-one, and
2-methyl-5-methoxymethyl-pyrazolo[1,5-a]pyrimidin-7-one;
6-Hydroxybenzomorpholine; and
3-Amino-2-methylamino-6-methoxypyridine;
1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one.
Preferred couplers include: phenol, resorcinol, and naphthol
derivatives such as: naphthalene-1,7-diol, benzene-1,3-diol,
4-chlorobenzene-1,3-diol, naphthalen-1-ol,
2-methyl-naphthalen-1-ol, naphthalene-1,5-diol,
naphthalene-2,7-diol, benzene-1,4-diol, 2-methyl-benzene-1,3-diol,
and 2-isopropyl-5-methylphenol; 1,2,4-Trihydroxybenzene;
1-Acetoxy-2-methylnaphthalene; and mixtures thereof;
m-phenylenediamine derivatives such as: benzene-1,3-diamine,
2-(2,4-diamino-phenoxy)-ethanol,
4-{3-[(2,4-diaminophenyl)oxy]-propoxy}benzene-1,3-diamine,
2-(3-amino-4-methoxy-phenylamino)-ethanol,
2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and
3-(2,4-diamino-phenoxy)-propan-1-ol;
2,4-Diamino-5-(2'-hydroxyethyloxy)toluene;
N,N-Dimethyl-3-ureidoaniline;
2,4-Diamino-5-fluorotoluenesulfatehydrate;
1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and mixtures thereof;
m-aminophenol derivatives such as: 3-amino-phenol,
5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol,
and 3-amino-2-methyl-phenol;
1-Methyl-2-hydroxy-4-(2'-hydroxyethyl)aminobenzene;
1-Hydroxy-3-amino-2,4-dichlorobenzene;
1,3-Bis-(2,4-Diaminophenoxy)propane;
1-Hydroxy-2-methyl-5-amino-6-chlorobenzene;
5-Amino-4-chloro-2-methylphenol; and mixtures thereof; and
heterocyclic derivatives such as:
3,4-dihydro-2H-1,4-benzoxazin-6-ol,
4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,
1,3-benzodioxol-5-ol, 1,3-benzodioxol-5-amine, 1H-indol4-ol,
1H-indole-5,6-diol, 1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,
1H-indole-2,3-dione, pyridine-2,6-diamine, 2-aminopyridin-3-ol,
4-hydroxy-N-methylindole, 1H-5-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one,
2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,
2,6-dimethyl[3,2-c]-1,2,4-triazole,
6-methylpyrazolo-[1,5-a]benzimidazole; 2,6-dihydroxypyridine;
2,6-dihydroxy-3,4-dimethylpyridine; 6-Hydroxybenzomorpholine;
2,6-Dihydroxy-3,4-dimethylpyridine;
3,5-Diamino-2,6-dimethoxypyridine;
3-Amino-2-methylamino-6-methoxypyridine;
1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;
and mixtures thereof.
More preferred couplers include: benzene-1,3-diol;
4-chlorobenzene-1,3-diol; 2-methyl-benzene-1,3-diol;
benzene-1,3-diamine; 3-amino-phenol; 5-amino-2-methyl-phenol;
1-Methyl-2-hydroxy-4-(2'-hydroxyethyl)aminobenzene;
4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one;
2-aminopyridin-3-ol; 1-phenyl-3-methylpyrazol-5-one;
1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;
and mixtures thereof.
Particularly preferred dyes for use herein include p-phenylene
diamine, p-aminophenol, o-aminophenol, 2,5-diaminotoluene sulphate,
p-methylaminophenol, N,N-bis-hydroxyethyl-p-phenylene diamine
sulphate, 4-amino-2,6-dichlorophenol, m-aminophenol,
4-amino-20hydroxytoluene, resorcinol, methylresorcinol, napthol,
2-amino-3-hydroxy pyridine, 2-amino-4-hydroxyethylamino anisole
sulphate, 2-methyl-5-hydroxyethylaminophenol, m-phenylenediamine
sulphate, 1-phenyl-3-methyl-5-pyrazolone,
1-hydroxyethyl-4,5-diamino pyrazole sulphate,
1-acetoxy-2-methylnapthalene and mixtures thereof.
The hair colouring compositions of the present invention may also
include non oxidative hair dyes i.e. direct dyes which may be used
alone or in combination with the above described oxidative dyes.
Suitable direct dyes include azo or anthraquinone dyes and nitro
derivatives of the benzene series and or melanin precursors and
mixtures thereof. Such direct dyes are particularly useful to
deliver shade modification or highlights.
The hair dye compositions of the present invention will generally
comprise from about 0.001% to about 10% of dyes. For example
compositions providing low intensity dyeing such as natural blond
to light brown hair shades generally comprise from about 0.001% to
about 5%, preferably from about 0.1% to about 2%, more preferably
from about 0.2% to about 1% by weight of dyeing composition of
precursors and couplers. Darker shades such as browns and black
typically comprise from 0.001% to about 10% by weight, preferably
from about 0.05% to about 7% by weight, more preferably form about
1% to about 5% of precursors and couplers.
Thickeners
The composition of the present invention may optionally further
comprise at least about 0.01% of thickeners. Thickeners are
preferably comprised in amount sufficient to provide the
composition with a viscosity of from about 1 Pa.s to 40 Pa.s (1,000
to 40,000 cP) at 26.degree. C. in order to provide a composition
that can be readily applied to the hair without dripping.
The at least one thickener is chosen, for example, from: (i)
associative thickeners; (ii) crosslinked acrylic acid homopolymers;
(iii) crosslinked copolymers of (meth)acrylic acid and of (C1
C6)alkyl acrylate; (iv) nonionic homopolymers and copolymers
containing ethylenically unsaturated monomers of ester and amide
type; (v) ammonium acrylate homopolymers and copolymers of ammonium
acrylate and of acrylamide; (vi) polysaccharides; (vii) C12 C30
fatty alcohols and (viii) particulate or crystalline
thickeners.
(i) As used herein, the expression "associative thickener" means an
amphiphilic thickener comprising both hydrophilic units and
hydrophobic units, for example, at least one C8 C30 fatty chain and
at least one hydrophilic unit. Representative associative
thickeners that may be used are associative polymers chosen
from:
(i) nonionic amphiphilic polymers comprising at least one fatty
chain and at least one hydrophilic unit;
(ii) anionic amphiphilic polymers comprising at least one
hydrophilic unit and at least one fatty-chain unit;
(iii) cationic amphiphilic polymers comprising at least one
hydrophilic unit and at least one fatty-chain unit; and
(iv) amphoteric amphiphilic polymers comprising at least one
hydrophilic unit and at least one fatty-chain unit;
The nonionic amphiphilic polymers comprising at least one fatty
chain and at least one hydrophilic unit may, for example, be chosen
from:
(1) celluloses modified with groups comprising at least one fatty
chain; for example: hydroxyethylcelluloses modified with groups
comprising at least one fatty chain chosen from alkyl, arylalkyl
and alkylaryl groups, and in which the alkyl groups are, for
example, C8 C22, such as the product Natrosol Plus Grade 330 CS(C16
alkyls) sold by the company Aqualon, and the product Bermocoll EHM
100 sold by the company Berol Nobel, and celluloses modified with
polyalkylene glycol alkylphenyl ether groups, such as the product
Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenyl
ether) sold by the company Amerchol.
(2) hydroxypropyl guars modified with groups comprising at least
one fatty chain, such as the product Esaflor HM 22 (C22 alkyl
chain) sold by the company Lamberti, and the products Miracare
XC95-3 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the
company Rhodia Chimie.
(3) polyether urethanes comprising at least one fatty chain, such
as C10 C30 alkyl or alkenyl groups, for instance the products
Elfacos T 210 and Elfacos T 212 sold by the company Akzo or the
products Aculyn 44 and Aculyn 46 sold by the company Rohm &
Haas.
(4) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic
monomers; examples that may be mentioned include: the products
Antaron V216 and Ganex V216 (vinylpyrrolidone/hexadecene copolymer)
sold by the company I. S. P. , the products Antaron V220 and Ganex
V220 (vinylpyrrolidone/eicosene copolymer) sold by the company I.
S. P.
(5) copolymers of C1 C6 alkyl acrylates or methacrylates and of
amphiphilic monomers comprising at least one fatty chain, such as
the oxyethylenated methyl methacrylate/stearyl acrylate copolymer
sold by the company Goldschmidt under the name Antil 208.
(6) copolymers of hydrophilic acrylates or methacrylates and of
hydrophobic monomers comprising at least one fatty chain, such as
polyethylene glycol methacrylate/lauryl methacrylate copolymer.
The anionic amphiphilic polymers comprising at least one
hydrophilic unit and at least one fatty-chain unit, may, for
example, be chosen from those comprising at least one fatty-chain
allyl ether unit and at least one hydrophilic unit comprising an
ethylenic unsaturated anionic monomeric unit, for example, a
vinylcarboxylic acid unit and further, for example, chosen from
units derived from acrylic acids, methacrylic acids and mixtures
thereof, wherein the fatty-chain allyl ether unit corresponds to
the monomer of formula below: CH2=C(R1)CH2OBnR (I)
in which R1 is chosen from H and CH3, B is an ethyleneoxy radical,
n is chosen from zero and integers ranging from 1 to 100, R is
chosen from hydrocarbon-based radicals chosen from alkyl,
arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising from
10 to 30 carbon atoms, and, further, for example, from 10 to 24
carbon atoms and even further, for example, from 12 to 18 carbon
atoms.
In one embodiment, a unit of formula (I) is, for example, a unit in
which R1 can be H, n can be equal to 10 and R can be a stearyl
(C18) radical.
Anionic amphiphilic polymers of this type are described and
prepared, according to an emulsion polymerization process, in
patent EP-0 216 479 B2.
In one embodiment, anionic amphiphilic polymers are, for example,
polymers formed from 20% to 60% by weight of acrylic acid and/or of
methacrylic acid, from 5% to 60% by weight of lower alkyl
(meth)acrylates, from 2% to 50% by weight of fatty-chain allyl
ether of formula (I), and from 0% to 1% by weight of a crosslinking
agent which is a well-known copolymerizable unsaturated
polyethylenic monomer, for example, diallyl phthalate, allyl
(meth)acrylate, divinylbenzene, (poly)ethylene glycol
dimethacrylate and methylenebisacrylamide.
Examples of such polymers are crosslinked terpolymers of
methacrylic acid, of ethyl acrylate and of polyethylene glycol (10
EO) stearyl ether (Steareth-10), such as those sold by the company
Ciba under the names Salcare SC 80 and Salcare SC 90, which are
aqueous 30% emulsions of a crosslinked terpolymer of methacrylic
acid, of ethyl acrylate and of steareth-10 allyl ether
(40/50/10).
The anionic amphiphilic polymers may further be chosen, for
example, from those comprising at least one hydrophilic unit of
unsaturated olefinic carboxylic acid type, and at least one
hydrophobic unit of the type such as a (C10 C30) alkyl ester of an
unsaturated carboxylic acid. The hydrophilic unit of unsaturated
olefinic carboxylic acid type corresponds to, for example, the
monomer of formula (II) below:
##STR00002##
in which R1 is chosen from H, CH3, and C2H5, i.e. acrylic acid,
methacrylic acid and ethacrylic acid units. And the hydrophobic
unit of the type such as a (C10 C30) alkyl ester of an unsaturated
carboxylic acid corresponds to, for example, the monomer of formula
(III) below:
##STR00003##
in which R1 is chosen from H, CH3, and C2H5 (i.e. acrylate,
methacrylate and ethacrylate units) and is, for example, chosen
from, for example, H (acrylate units) and CH3 (methacrylate units),
R2 is chosen from C10 C30 alkyl radicals, for example, C12 C22
alkyl radical.
Examples of (C10 C30)alkyl esters of unsaturated carboxylic acids
include lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl
acrylate, and dodecyl acrylate, and the corresponding
methacrylates, lauryl methacrylate, stearyl methacrylate, decyl
methacrylate, isodecyl methacrylate and dodecyl methacrylate.
Anionic amphiphilic polymers of this type are disclosed and
prepared, for example, according to U.S. Pat. Nos. 3,915,921 and
4,509,949.
Representative anionic amphiphilic polymers that can be used may
further be chosen from polymers formed from a mixture of monomers
comprising:
(i) acrylic acid, an ester of formula (IV) below:
##STR00004##
in which R1 is chosen from H and CH3, R2 is chosen from C10 C30
alkyl radicals, such as alkyl radicals comprising from 12 to 22
carbon atoms, and a crosslinking agent; such as polymers derived
from 95% to 60% by weight of the acrylic acid (hydrophilic unit),
4% to 40% by weight of C10 C30 alkyl acrylate (hydrophobic unit),
and 0% to 6% by weight of crosslinking polymerizable monomer, or
polymers derived from 98% to 96% by weight of the acrylic acid
(hydrophilic unit), 1% to 4% by weight of C10 C30 alkyl acrylate
(hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking
polymerizable monomer; or
(ii) acrylic acid and lauryl methacrylate, such as the polymers
formed from 66% by weight of acrylic acid and 34% by weight of
lauryl methacrylate.
The crosslinking agent can be a monomer comprising a group (V)
##STR00005##
with at least one other polymerizable group whose unsaturated bonds
are not conjugated with respect to one another. Mention may be
made, for example, of polyallyl ethers such as polyallylsucrose and
polyallyl pentaerythritol.
Among said polymers above mention may be made, for example, of the
products sold by the company Noveon under the trade names Pemulen
TR1, Pemulen TR2, Carbopol 1382, and further, for example, Pemulen
TR1, and the product sold by the company S. E. P. C. under the name
Coatex SX.
Suitable anionic amphiphilic fatty-chain polymers, include for
example the methacrylic acid/methyl acrylate/ethoxylated alkyl
dimethyl-meta-isopropenylbenzylisocyanate copolymer sold under the
name Viscophobe DB 1000 by the company Amerchol.
The cationic amphiphilic polymers used are, for example, chosen
from quaternized cellulose derivatives and polyacrylates comprising
amino side groups.
The quaternized cellulose derivatives are, for example, chosen
from; quaternized celluloses modified with groups comprising at
least one fatty chain, such as alkyl, arylalkyl and alkylaryl
groups comprising at least 8 carbon atoms, and mixtures thereof,
quaternized hydroxyethylcelluloses modified with groups comprising
at least one fatty chain, such as alkyl, arylalkyl and alkylaryl
groups comprising at least 8 carbon atoms, and mixtures
thereof.
Quaternized and non-quaternized polyacrylates comprising amino side
groups having for example, hydrophobic groups, such as Steareth 20
(polyoxy-ethylenated(20) stearyl alcohol) and (C10 C30)alkyl PEG-20
itaconate.
The alkyl radicals borne by the above quaternized celluloses and
hydroxyethylcelluloses, for example, contain from 8 to 30 carbon
atoms. The aryl radicals, for example, are chosen from phenyl,
benzyl, naphthyl and anthryl groups.
Examples of quaternized alkylhydroxyethyl-celluloses comprising C8
C30 fatty chains are the products Quatrisoft LM 200, Quatrisoft
LM-X 529-18-A, Quatrisoft LM-X 529-18B (C12 alkyl) and Quatrisoft
LM-X 529-8 (C18 alkyl) sold by the company Amerchol, and the
products Crodacel QM, Crodacel QL (C12 alkyl) and Crodacel QS (C18
alkyl) sold by the company Croda.
Examples of polyacrylates comprising amino side chains is Structure
Plus from the company National Starch.
Among amphoteric amphiphilic polymers comprising at least one
hydrophilic unit and at least one fatty-chain unit, mention may be
made, for example, of methacrylamidopropyltrimethylammonium
chloride/acrylic acid/C10 C30 alkyl methacrylate copolymers,
wherein the alkyl radical is, for example, a stearyl radical.
(ii) Among the crosslinked acrylic acid homopolymers that may be
mentioned are those crosslinked with an allylic alcohol ether of
the sugar series, such as the products sold under the names
Carbopol 980, 981, 954, 2984 and 5984 by the company Noveon or the
products sold under the names Synthalen M, Synthalen L and
Synthalen K by the company 3V Sigma.
(iii) Crosslinked copolymers of (meth)acrylic acid and of C1 C6
alkyl acrylate can be chosen from crosslinked copolymers of
methacrylic acid and of ethyl acrylate as an aqueous dispersion
comprising 38% active material sold, for example, under the name
Viscoatex 538C by the company Coatex, and crosslinked copolymers of
acrylic acid and of ethyl acrylate as an aqueous dispersion
comprising 28% active material sold under the name Aculyn 33 by the
company Rohm & Haas. Crosslinked copolymers of methacrylic acid
and of ethyl acrylate include an aqueous dispersion comprising 30%
active material manufactured and sold under the name Carbopol Aqua
SF-1 by the company Noveon.
(iv) Among the nonionic homopolymers or copolymers comprising
ethylenically unsaturated monomers of ester and/or amide type,
mention may be made of the products sold under the names: Cyanamer
P250 by the company Cytec (polyacrylamide); PMMA MBX-8C by the
company US Cosmetics (methyl methacrylate/ethylene glycol
dimethacrylate copolymer); Acryloid B66 by the company Rohm &
Haas (butyl methacrylate/methyl methacrylate copolymer); BPA 500 by
the company Kobo (polymethyl methacrylate).
(v) Ammonium acrylate homopolymers that may be mentioned include
the product sold under the name Microsap PAS 5193 by the company
Hoechst.
Copolymers of ammonium acrylate and of acrylamide include the
product sold under the name Bozepol C Nouveau or the product PAS
5193 sold by the company Hoechst (which are described and prepared
in documents FR-2 416 723, U.S. Pat. Nos. 2,798,053 and
2,923,692).
(vi) The polysaccharides are, for example, chosen from glucans,
modified and unmodified starches (such as those derived, for
example, from cereals, for instance wheat, corn or rice, from
vegetables, for instance yellow pea, and tubers, for instance
potato or cassaya), amylose, amylopectin, glycogen, dextrans,
celluloses and derivatives thereof (methylcelluloses,
hydroxyalkylcelluloses, ethyl hydroxyethylcellu loses, and
carboxymethylcelluloses), mannans, xylans, lignins, arabans,
galactans, galacturonans, chitin, chitosans, glucuronoxylans,
arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins,
alginic acid and alginates, arabinogalactans, carrageenans, agars,
glycosaminoglucans, succinoglucans, gum arabics, gum tragacanths,
ghatti gums, karaya gums, carob gums, galactomannans, such as guar
gums, and nonionic derivatives thereof (hydroxypropyl guar) and
xanthan gums, and mixtures thereof.
For example, suitable polysaccharides are described in
"Encyclopedia of Chemical Technology", Kirk-Othmer, Third Edition,
1982, volume 3, pp. 896 900, and volume 15, pp. 439 458, in
"Polymers in Nature" by E. A. MacGregor and C. T. Greenwood,
published by John Wiley & Sons, Chapter 6, pp. 240 328,1980,
and in "Industrial Gums--Polysaccharides and their Derivatives",
edited by Roy L. Whistler, Second Edition, published by Academic
Press Inc., the content of these three publications being entirely
incorporated by reference.
For example, starches, guar gums and celluloses and derivatives
thereof can be used. Suitable starches include for example, of
macromolecules in the form of polymers comprising elemental
moieties that are anhydroglucose units. The number of these
moieties and their assembly make it possible to distinguish between
amylose (linear polymer) and amylopectin (branched polymer). The
relative proportions of amylose and of amylopectin, and also their
degree of polymerization, can vary as a function of the botanical
origin of the starches. The botanical origin of the starch
molecules used may be cereals or tubers. Thus, the starches can be,
for example, chosen from corn starch, rice starch, cassaya starch,
tapioca starch, barley starch, potato starch, wheat starch, sorghum
starch and pea starch. Starches are generally in the form of a
white powder, which is insoluble in cold water and which has an
elementary particle size ranging from 3 to 100 microns. The
starches may optionally be C1 C6 hydroxyalkylated or C1 C6 acylated
(such as acetylated). The starches may also have undergone heat
treatments. Distarch phosphates or of compounds rich in distarch
phosphate, for instance the products sold under the references
Prejel VA-70-T AGGL (gelatinized hydroxypropylated cassaya distarch
phosphate) or Prejel TK1 (gelatinized cassaya distarch phosphate)
or Prejel 200 (gelatinized acetylated cassaya distarch phosphate)
by the company Avebe, or Structure ZEA from National Starch
(hydroxypropylated corn distarch phosphate), Structure XL from
National Starch (hydroxypropylated starch phosphate) may also be
used.
The guar gums may be modified or unmodified. The unmodified guar
gums are, for example, the products sold under the name Vidogum GH
175 by the company Unipectine and under the names Meyro-Guar 50 and
Jaguar C by the company Meyhall. The modified nonionic guar gums
are, for example, modified with C1 C6 hydroxyalkyl groups. Among
hydroxyalkyl groups, mention may be made, for example, of
hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
These guar gums are well known in the state of the art and can be
prepared, for example, by reacting corresponding alkene oxides,
such aspropylene oxides, with guar gum so as to obtain a guar gum
modified with hydroxypropyl groups. The degree of
hydroxyalkylation, which corresponds to the number of alkylene
oxide molecules consumed by the number of free hydroxyl functions
present on the guar gum, may, for example, range from 0.4 to
1.2.
Such nonionic guar gums optionally modified with hydroxyalkyl
groups are sold, for example, under the trade names Jaguar HP8,
Jaguar HP60 and Jaguar HP120, Jaguar DC 293 and Jaguar HP 105 by
the company Rhodia Chimie (Meyhall) or under the name Galactasol
4H4FD2 by the company Aqualon.
Suitable celluloses include for example, hydroxyethylcellulose and
hydroxypropylcelluloses, such as the products sold under the names
Klucel EF, Klucel H, Klucel LHF, Klucel MF and Klucel G by the
company Aqualon.
(vii) The C12 C30 fatty alcohols are, for example, chosen from
myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol
or mixture thereof. When fatty alcohols are used as thickeners, at
least one additional surfactant with HLB value above about 6 is
commonly included to form bi-layers with fatty alcohols. The most
useful bi-layer structures include gel network phase where parallel
bi-layers of fatty alcohols are swollen by water forming semi-solid
creams, and vesicle dispersions where fatty alcohols bi-layers are
curved into approximately spherical uni-lamellar or multi-lamellar
aggregates.
(viii) The particulate and crystalline thickeners are for example,
clays, fumed silica, microcrystalline cellulose, trihydroxystearin
(ThixcinR), ethyleneglycol mono- and di-stearate or mixture
thereof. The particulate or crystalline thickeners work via
mechanisms well known in the art, for example particle aggregation,
"house of card" particle arrangement or crystalline fiber
formation.
Conditioning Agent
The compositions of the present invention may comprise or are used
in combination with a composition comprising a conditioning agent.
Conditioning agents suitable for use herein are selected from
silicone materials, amino silicones, fatty alcohols, polymeric
resins, polyol carboxylic acid esters, cationic polymers, cationic
surfactants, insoluble oils and oil derived materials and mixtures
thereof. Additional materials include mineral oils and other oils
such as glycerin and sorbitol.
The conditioning agent will generally be used at levels of from
about 0.05% to about 20% by weight of the composition, preferably
of from about 0.1% to about 15%, more preferably of from about 0.2%
to about 10%, even more preferably of from about 0.2% to about
2%.
Particularly useful conditioning materials are cationic polymers.
Conditioners of cationic polymer type may be chosen from those
already know by those skilled in the art as improving at least one
cosmetic properties of keratin fibres treated with a cosmetic
composition. Cationic polymers can be chosen from those comprising
units of at least one amine group chosen from primary, secondary,
tertiary and quaternary amine groups that may either form part of
the main polymer chain, or be borne by a side substituant that is
directly attached to the main polymer chain. Such cationic polymers
generally have a number average molecular mass ranging from 500 to
5.times.10.sup.6, or more preferably from 1000 to 3.times.10.sup.6.
Polymers of the polyamine, polyamino amide and polyquaternary
ammonium type that may be used include but are not limited to: 1)
homopolymers and copolymers derived from acrylic or methacrylic
esters or amides. Copolymers of these polymers can also comprise at
least one unit derived from comonomers which may be chosen from the
family of acrylamides, methacrylamides, diacetone acylamides,
acrylamides and methacrylicamides substituted on the nitrogen with
at least one group chosen from lower (C1 C4) alkyls, acrylic and
methacrylic acids and esters thereof, vinlylactams such as
vinlypyrrolidone and vinylcaprolactam, and vinyl esters. Examples
of such polymers include:
Copolymers of acrylamide and of
methacryloyloxyethyltrimethylammonium methosulfate, examples of
which include polymers known via the INCI nomenclature as
Polquaternium-5, such as the products sold under the names Reten
210, Reten 220, Reten 230, Reten 240, Reten 1104, Reten 1105, Reten
1006 by the company Hercules and Merquat 5, Merquat 5 SF by the
company Nalco.
Copolymers of vinylpyrrolidone and dimethylaminopropyl
methacrylamide, examples of which include polymers known via the
INCI nomenclature as Polyquaternium-28, such as the products sold
under the name Gafquat HS-100 by the company International
Speciality Products (ISP).
Coplolymers of vinyl pyrrolidone and dialkyaminoalkyl acrylates or
methactylates, examples of which include polymers known via the
INCI nomenclature as Polquaternium-11, such as the products sold
under the name Gafquat 440, Gafquat 734, Gafquat 755, Gafquat 755N
by the company International Speciality Products (ISP), and
Luviquat PQ11 PM by the company BASF and Polyquat-11 SL by the
company Sino Lion.
Copolymers vinylpyrrolidone, dimethylaminopropyl methacrylamide and
methacryloylaminopropyl lauryldimonium chloride, examples of which
include polymers known via the INCI nomenclature as
polyquaternium-55, such as the products sold under the name Styleze
W-20 by the company International Speciality Products (ISP).
Copolymers of acrylic acid, acrylamide and
methacrylamidopropyltrimonium chloride, examples of which include
polymers known via the INCI nomenclature as Polyquaternium-53, such
as the products sold under the name Merquat 2003 by the company
Nalco.
Copolymers of dimethyaminopropylacrylate (DMAPA), acrylic acid and
acrylonitrogens and diethyl sulfate, examples of which include
polymers known via the INCI nomenclature as Polyquaternium-31, such
as the products sold under the name Hypan QT100 by the company
Lipo.
Copolymers of acrylamide, acrylamidopropyltrimonium chloride,
2-amidopropylacrylamide sulfonate, and dimethyaminopropylacrylate
(DMAPA), examples of which include polymers known via the INCI
nomenclature as polyquaternium43, such as the products sold under
the name Bozequat 4000 by the company Clairant.
Copolymers of acrylic acid, methylacrylate and
methacrylamidopropyltrimonium chloride, examples of which include
polymers known via the INCI nomenclature as Polyquaternium-47, such
as the products sold under the name Merquat 2001 and Merquat 2001N
sold commercially by Nalco.
Copolymes of methacryloyl ethyl betaine, 2-hydroxyethyl
methacrylate and methacryloyl ethyl trimethyl ammonium chloride,
examples of which include polymers known via the INCI nomenclature
as Polyquaternium-48, such as the products sold under the name
Plascize L450 by the company Goo Chemcial.
Copolymers of acrylic acid diallyl dimethyl ammonium chloride and
acrylamide, examples of which include polymers known via the INCI
nomenclature as polyquaternium 39, such as the products sold under
the name Merquat 3330 and Merquat 3331 by the company Nalco.
Further examples include copolymers of methacrylamide
methacrylamido-propyltrimonium and methacryloylethyltrimethyl
ammonium chloride and their derivatives, either homo or
copolymerised with other monomers, examples of which include
polymers known via the INCI nomenclature as: Polyquaternium-8,
Polyquaternium-9, Polyquaternium-12, Polyquaternium-13
Polyquaternium-14, Polyquaternium-15, such as the products sold
under the name Rohagit KF 720 F by the company Rohm,
Polyquaternium-30, such as the products sold under the name
Mexomere PX by the company Chimex, Polyquatemium-33,
Polyquaternium-35, Polyquaternium-36, such as the products sold
under the name Plex 3074 L by the company Rhon, Polyquaternium 45,
such as the products sold under the name Plex 3073L by the company
Rohn, Polyquaternium 49, such as the products sold under the name
Plascize L440 by the company Goo Chemicals, Polyquaternium 50 such
as the products sold under the name Plascize L441 by the company
Goo Chemicals, Polyquaternium-52. 2) Cationic polysaccharides, such
as cationic celluloses and cationic galactomannan gums. Among the
cationic polysaccharides that maybe mentioned, for example, are
cellulose ether derivatives comprising quaternary ammonium groups
and cationic cellulose copolymers or cellulose derivatives grafted
with a water-soluble quaternary ammonium monomer and cationic
galactomannan gums. Examples include but are not limited to
Copolymers of hydroxyethylcelluloses and diallyldimethyl ammonium
chlorides, examples of which include polymers known via the INCI
nomenclature as Polyquaternium-4, such as the products sold under
the name Celquat L 200 and Celquat H 100 by the company National
Starch.
Copolymers of hydroxyethylcelluloses and a trimethyl ammonium
substituted epoxide, examples of which include polymers known via
the INCI nomenclature as Polyquaternium-10, such as the products
sold under the name AEC Polyquaternium-10 by the company A&E
Connock , Catinal C-100 Catinal HC-35 Catinal HC-100 Catinal HC-200
Catinal LC-100 Catinal LC-200 by the company Toho, Celquat SC-240C
Celquat SC-230M, by the company National Starch, Dekaquat 400,
Dekaquat 3000 by the company Dekker, Leogard G P by the company
Akzo Nobel, RITA Polyquta 400 RITA, Polyquta 3000 by the company
RITA, UCARE Polymer JR-125 UCARE Polymer JR-400 UCARE Polymer
JR-30M UCARE Polymer LK UCARE Polymer LR 400 UCARE Polymer LR 30M
by the company Amerchol.
Copolymers of hydroxyethylcelluloses and lauryl dimethyl ammonium
substituted epoxides, examples of which include polymers known via
the INCI nomenclature as Polyquaternium-24, such as the products
sold under the name Quatrisoft polymer LM-200 by the company
Amerchol.
Derivatives of Hydroxypropyl Guar, examples of which include
polymers known via the INCI nomenclature as Guar
Hydroxypropyltrimonium Chloride, such as the products sold under
the name Catinal CG-100, Catinal CG-200 by the company Toho,
Cosmedia Guar C-261N, Cosmedia Guar C-261N, Cosmedia Guar C-261N by
the company Cognis, DiaGum P 5070 by the company Freedom Chemical
Diamalt, N-Hance Cationic Guar by the company Hercules/Aqualon,
Hi-Care 1000, Jaguar C-17, Jaguar C-2000, Jaguar C-13S, Jaguar
C-14S, Jaguar Excel by the company Rhodia, Kiprogum CW, Kiprogum
NGK by the company Nippon Starch.
Hydroxypropyl derivatives of Guar Hydroxypropyltrimonium Chloride,
examples of which include polymers known via the INCI nomenclature
as Hydroxypropyl Guar Hydroxypropyltrimonium Chloride, such as the
products sold under the name Jagaur C-162 by the company Rhodia. 3)
Polyamino amide derivatives resulting from the condensation of
polyalkylene polyamines with polycarboxylic acids followed by
alkylation with difunctional agents. Among the derivative, mention
may be made for example to adipic
acid/dimethylaminohydroxypropyl/diethylenetriamine. 4) Polymers
obtained by reaction of a polyalkylene polyamine comprising two
primary amines groups and at last one secondary amine group with a
decarboxylic acid chosen from diglycolic acids and saturated
aliphatic dicarboxylic acids comprising from 3 to 8 carbon atoms.
Non-limiting examples of such derivatives include the adipic
acid/epxoypropyl/diethylenetriamine. 5) Cyclopolymers of
dialkdiallylamine or of dialkyldiallyammonium, among which polymers
mention may be made of:
Dimethyldiallyammonium chloride polymers, examples of which include
polymers known via the INCI nomenclature as Polyquaternium-6, such
as the products sold under the name Merquat 100 by the company
Nalco, Mirapol 100 by the company Rhodia, Rheocare CC6 by the
company Cosmetic Rheologies, AEC polyquaternium-6 by the company
A&E Connock, Agequat 400 by the company CPS, Conditioner P6 by
the company 3V Inc., Flocare C106 by the company SNF, Genamin PDAC
by the company Clariant, Mackernium 006 by the company
McIntyre.
Copolymers of acrylamides and dimethyldiallylammonium chlorides
monomers, examples of which include polymers known via the INCI
nomenclature as Polyquaternium-7, such as the products sold under
the name AEC Polyquaternium-7 by the company A&E Connock,
Agequat-5008, Agequat C-505 by the company CPS, Conditioner P7 by
the company 3V Inc. Flocare C 107 by the company SNF Mackernium
007, Mackernium 007S by the company McIntyre, ME Polymer 09W by the
company Toho, Merquat 550, Merquat 2200, Merquat S by the company
Nalco, Mirapol 550 by the company Rhodia, Rheocare CC7, Rheocare
CCP7 by the company Cosmetic Rheologies, Salcare HSP-7, Salcare
SC10, Salcare Super 7 by the company Ciba.
Copolymers of dimethyldiallylammoniumchlorides and acrylic acids,
examples of which include polymers known via the INCI nomenclature
as polyquaternary-22, such as the products sold under the name
Merquat 280 and Merquat 295 by the company Nalco. 6) Quaternary
diammonium polymers comprising repeat units corresponding to
[--N+(R1)(R2)-A1-N+(R3)(R4)-B1-][2X--], in which R1, R2, R3 and R4,
which may be identical or different, are chosen from aliphatic,
alicyclic and arylaliphatic radicals comprising from 1 to 20 carbon
atoms and from lower hydroxyalkylaliphatic radicals, or R1, R2, R3
and R4, together or separately, constitute, with the nitrogen atoms
to which they are attached, heterocycles optionally comprising a
second heteroatom other then nitrogen, or R1, R2, R3 and R4, are
choen from liner or branched C1 C6 alkyl radicals substituted with
at least one group chosen from nitrile, ester, acyl and amide
groups and groups of --CO--O--R5-D and --CO--NH--R5-D wherein R5 is
chosen from alkylene groups and D is chosen from quaternary
ammonium groups. A1and B1, which may be identical or different, are
chosen from linear and branched, saturated or unsaturated
polymethylene groups comprising 2 to 20 carbon atoms. The
polymethylene groups may comprise, linked to or intercalated in the
main ring, at least one entity chosen from aromatic rings, oxygen
and sulphur atoms and sulphoxide, sulphone, disulphide, amino,
alkylamino, hydroxyl, quaternary, ammonium, ureido, amide and ester
groups, and X-- is an anion derived from inorganic and organic
acids. D is chosen from a glycol residue, a bis-secondary diamine
residue, a bis-primary diamine residue or a ureylene group. An
examples of which include polymers known via the INCI nomenclature
as Hexadimethrine chloride, where R1, R2, R3 and R4 are each methyl
radicals, A1 is (CH2)3 and B1 is (CH2)6 and X.dbd.C1. Further
examples of which include polymers known via the INCI nomenclature
as polyquaternium-34 where R1 and R2 are ethyl radicals and R3 and
R4 are methyl radicals and A1 is (CH2)3 and B1 is (CH2)3 and
X.dbd.Br, such as the products sold under the name Mexomere PAX by
the company Chimax. 7) Polyquaternary ammonium polymers comprising
repeating units of formula [--N+(R6)(R7)-(CH2)
r-NH--CO--(CH2)q-(CO)t-NH--(CH2)s-N+(R8)(R9)-A-][2X--], in which
R6, R7, R8 and R9 which may be identical or different, are chosen
from a hydrogen atom and a methyl, ethyl, propyl, hydroxyethyl,
hydroxypropyl, and --CH2CH2(OCH2CH2)pOH radicals, wherein p is
equal to 0 or an integer ranging from 1 to 6, wherein R6, R7, R8
and R9 do not all simultaneously represent a hydrogen atom. R and s
which maybe identical or different are each an integer ranging from
1 to 6, q is equal to 0 or an integer ranging from 1 to 34 and X--
is anion such as a halide. T is an integer chosen to be equal to 0
or 1. A is chosen from divalent radicals such as
--CH2-CH2-O--CH2-CH2-. Examples of which include
Polymers known via the INCI nomenclature as polyquaternium-2, where
r=s=3, q=0,t=0, R6,R7, R8 and R9 are methyl groups, and A is
--CH2-CH2-O--CH2-CH2, such as the products sold under the name
Ethpol PQ-2 from Ethox and Mirapol A-15 by the company Rhodia.
Polymers known via the INCI nomenclature as polyquaternium-17 where
r=s=3, q=4, t=1 R6, R7, R8 and R9 are methyl groups, and A is
--CH2-CH2-O--CH2-CH2.
Polymers known via the INCI nomenclature as Polyquaternium 18,
where r=s=3, q=7, t=1 R6, R7, R8 and R9 are methyl groups, and A is
--CH2-CH2-O--CH2-CH2
Polymers known via the INCI nomenclature as the block copolymer
formed by the reaction of Polyquatemium-2 with Polyquaternium-17,
known as Polyquaternium 27, such as the products sold under the
name Mirapol 175 by the company Rhodia.
8) Copolymers of vinylpyrrolidones and of vinylimidazoles and
optionally vinylcaprolactums, examples of which include polymers
known via the INCI nomenclature as Polyquatemary-16 formed from
methylvinylimidazolium chlorides and vinylpyrrolidones, such as the
products sold under the name Luviquat FC370, Luviquat FC550,
Luviquat FC905, Luviquat HM-552 by the company BASF. Or copolymers
of vinylcaprolactams and vinylpyrrolidones with
methylvinylimidazolium methosulfates, examples of which include
polymers known via the INCI nomenclature as Polyquaternium-46, such
as the products sold under the name Luviquat Hold by the company
BASF. Or copolymers of vinylpyrrolidones and quatemized
imidazolines, examples of which include polymers known via the INCI
nomenclature poylquaterary 44, such as the products sold under the
name Luviquat Care by the company BASF 9) Polyamines such as the
product Polyquart H sold by Cognis under the reference name
polyethylene glycol (15) tallow polyamine in the CTFA dictionary.
10) Cross linked methacryloyloxy(C1 C4)alkyltri(C1 C4)alkylammonium
salt polymers such as the polymers obtained by homopolymerisation
of dimethylaminoethyl methacrylates quaternized with methyl
chloride, or by copolymerisation of acrylamides with
dimethylaminoethyl methacrylates quaternized with methyl chloride,
the homo or copolymerisation being followed by crosslinking with a
compound comprising olefinic unsaturation, such as
methylenebisacrylamides, examples of which include polymers known
via the INCI nomenclature as Polyquaternium-37, such as the
products sold under the name Synthalen, CN Synthalen CR, Synthalen
CU, sold by 3V sigma, or as a dispersion in another media such as
the products sold under the name Salcare SC95 and Salcare SC96 by
the company Ciba or Rheocare CTH(E) by the company Cosmetic
Rheologies. Or in another example of which include polymers known
via the INCI nomenclature as Polyquaternium-32, or when sold as a
dispersion in mineral oil such as the products sold under the name
Salcare SC92 by the company Ciba. 11) Further examples of cationic
polymers include polymers known via the INCI nomenclature as
Polyquaternium 51, such as the products sold under the name
Lipidure-PMB by the company NOF, via the INCI nomenclature as
Polyquaternium 54, such as the products sold under the name
Qualty-Hy by the company Mitsui, and via the INCI nomenclature as
Polyquaternium 56 such as the products sold under the name Hairrol
UC4 by the company Sanyo chemicals. 12) silicone polymers
comprising cationic groups and/or groups which may be ionised into
cationic groups. For example: cationic silicones of the general
formula (R10-N+(CH3)2)-R11-(Si(CH3)2-O)x-R11-(N+(CH3)2)-R10), where
R10 is an alkyl derived from coconut oil, and R11 is
(CH2CHOCH2O(CH2)3 and x is a number between 20 and 2000, examples
of which include polymers known by the INCI nomenclature as
Quaternium 80, such as the products sold under the name as Abil
Quat 3272 and Abil Quat 3474 sold commercially by Goldschmidt.
Silicones containing groups which may be ionised into cationic
groups, for example aminosilicones containing at least 10 repeating
siloxane --(Si(CH3)2-O) units within the polymer chain, with either
terminal, graft or a mixture of terminal and graft aminofunctional
groups. Example functional groups are not limited to
aminoethylaminopropyl, aminoethylaminoisobutly, aminopropyl. In the
case of graft polymers, the terminal siloxane units can either be
(CH3)3Si--O or R12(CH3)2Si--O, where R12 can be either OH or OR13,
where R13 is a C1 C8 alky group, or a mixture of both functional
terminal groups. These silicones are also available as preformed
emulsions. Polymer with terminal siloxane units of (CH3)3Si--O
examples of which include polymers known by the INCI nomenclature
as trimethylsilylamodimethicone, such as the products sold under
the name as DC-2-8566, DC 7224 and DC-2-8220 sold commercially by
Dow Corning and SF1708 and SM 2125 sold commercially by GE
Silicones and Wacker Belsil ADM 653 sold commercially by Wacker
silicones. Further examples include polymers with terminal siloxane
units of (R12O)(CH3)2Si--O where R12 can be either OH or OR13,
where R13 is a C1 C8 alky group, or a mixture of both functional
terminal groups, known by the INCI nomenclature as amodimethicone,
such as the products sold under the name as Wacker Belsil ADM 1100,
Wacker Belsil ADM 1600, Wacker Belsil ADM 652, Wacker Belsil ADM
6057E, Wacker Belsil ADM 8020 sold commercial by Wacker Silicones,
DC929, DC939 and DC949 sold commercially by Dow Corning and SM2059
sold commercially by GE silicones.
Silicones containing groups which may be ionised into cationic
groups--for example silicones containing at least 10 repeating
siloxane --Si(CH3)2-O) units within the polymer chain, with either
terminal, graft or a mixture of terminal and graft aminofunctional
groups, together with additional functional groups. Additional
functional groups can include polyoxyalkylene, the reaction product
of amines and carbinols, alky chains. For example products know by
the INCI nomenclature as methoxy PEG/PPG-7/3 Aminopropyl
Dimethicone, such as the product sold under the name of Abil Soft
AF100 sold commercially by Degussa. For example products know by
the INCI nomenclature as Bis (C13 15 Alkoxy) PG Amodimethicone,
such as the product sold under the name of DC 8500 sold
commercially by Dow Coming.
Surfactants
The compositions according to the present invention may further
comprise one or more surfactants. Surfactants suitable for use
herein generally have a lipophilic chain length of from about 8 to
about 30 carbon atoms and can be selected from anionic, nonionic,
amphoteric and cationic surfactants and mixtures thereof. The total
level of surfactant is from about 1% to about 60%, preferably from
about 2% to about 30%, more preferably from about 8% to about 25%
and especially from about 10% to about 20% by weight.
The compositions of the invention preferably comprise a mixture of
anionic and amphoteric surfactants with one or more nonionic
surfactants. Anionic components, where may be present in the range
of from about 0.1% to about 20%, preferably from about 0.1% to
about 15%, and more preferably from about 5% to about 15% by weight
of the composition; amphoteric or nonionic components, may
independently be present is in the range from about 0.1% to about
15% by weight, preferably from about 0.5% to about 10%, more
preferably from about 1% to about 8% by weight.
As examples of anionic surfactants, which can be used, alone or as
mixtures, mention may be made, for example, of salts (such as
alkaline salts, for example, sodium salts, ammonium salts, amine
salts, amino alcohol salts and magnesium salts) of the following
compounds: alkyl sulphates, alkyl ether sulphates, alkylamido ether
sulphates, alkylarylpolyether sulphates, monoglyceride sulphates;
alkyl sulphonates, alkyl phosphates, alkylamide sulphonates,
alkylaryl sulphonates, a-olefin sulphonates, paraffin sulphonates;
alkyl sulphosuccinates, alkyl ether sulphosuccinates, alkylamide
sulphosuccinates; alkyl sulphosuccinamates; alkyl sulphoacetates;
alkyl ether phosphates; acyl sarcosinates; acyl isethionates and
N-acyltaurates. The alkyl or acyl radical of all of these various
compounds, for example, comprises from 8 to 24 carbon atoms, and
the aryl radical, for example, is chosen from phenyl and benzyl
groups. Among the anionic surfactants, which can also be used,
mention may also be made of fatty acid salts such as the salts of
oleic, ricinoleic, palmitic and stearic acids, coconut oil acid or
hydrogenated coconut oil acid; acyl lactylates in which the acyl
radical comprises from 8 to 20 carbon atoms. Weakly anionic
surfactants can also be used, such as alkyl-D-galactosiduronic
acids and their salts, as well as polyoxyalkylenated (C.sub.6 C24)
alkyl ether carboxylic acids, polyoxyalkylenated (C.sub.6 C.sub.24)
alkylaryl ether carboxylic acids, polyoxyalkylenated (C.sub.6
C.sub.24) alkylamido ether carboxylic acids and their salts, for
example, those comprising from 2 to 50 ethylene oxide groups, and
mixtures thereof. Anionic derivatives of polysaccharides, for
example carboxyalkyl ether of alkyl polyglucosides, can be also
used.
The nonionic surfactants are compounds that are well known (see,
for example, in this respect "Handbook of Surfactants" by M. R.
Porter, published by Blackie & Son (Glasgow and London), 1991,
pp. 116 178). They can be chosen, for example, from
polyethoxylated, polypropoxylated and polyglycerolated fatty acids,
alkyl phenols, a-diols and alcohols comprising a fatty chain
comprising, for example, from 8 to 18 carbon atoms, it being
possible for the number of ethylene oxide or propylene oxide groups
to range, for example, from 2 to 200 and for the number of glycerol
groups to range, for example, from 2 to 30. Mention may also be
made of copolymers of ethylene oxide and of propylene oxide,
condensates of ethylene oxide and of propylene oxide with fatty
alcohols; polyethoxylated fatty amides preferably having from 2 to
30 mol of ethylene oxide and their momoethanolamine and
diethanolamine derivatives, polyglycerolated fatty amides, for
example, comprising on average from 1 to 5, and such as from 1.5 to
4, glycerol groups; polyethoxylated fatty amines such as those
containing from 2 to 30 mol of ethylene oxide; oxyethylenated fatty
acid esters of sorbitan having from 2 to 30 mol of ethylene oxide;
fatty acid esters of sucrose, fatty acid esters of polyethylene
glycol, alkylpolyglycosides, N-alkylglucamine derivatives, amine
oxides such as (C.sub.10 C.sub.14)alkylamine oxides or
N-acylaminopropylmorpholine oxides.
The amphoteric surfactants can be chosen, for example, from
aliphatic secondary and tertiary amine derivatives in which the
aliphatic radical is chosen from linear and branched chains
comprising from 8 to 22 carbon atoms and comprising at least one
water-soluble anionic group (for example carboxylate, sulphonate,
sulphate, phosphate or phosphonate); mention may also be made of
(C.sub.8 C.sub.20)alkylbetaines, sulphobetaines, (C.sub.8
C.sub.20)alkylamido(C.sub.1 C.sub.6) alkylbetaines or (C.sub.8
C.sub.20)alkylamido(C.sub.1 C.sub.6)alkylsulphobetaines.
Among the amine derivatives, mention may be made of the products
sold under the name Miranol, as described, for example,. in U.S.
Pat. Nos. 2,528,378 and 2,781,354 and having the structures of:
R.sub.2--CON
HCH.sub.2CH.sub.2--N.sup.+(R.sub.3)(R.sub.4)(CH.sub.2COO.sup.-)
(VI) in which: R.sub.2 is chosen from alkyl radicals derived from
an acid R.sub.2--COOH present in hydrolysed coconut oil, and
heptyl, nonyl and undecyl radicals, R.sub.3 is a
.beta.-hydroxyethyl group and R.sub.4 is a carboxymethyl group; and
of R.sub.5--CONHCH.sub.2CH.sub.2--N(B)(C) (VII) wherein B
represents --CH.sub.2CH.sub.2OX', C represents
--CH.sub.2).sub.z--Y', with z=1 or 2, X' is chosen from the
--CH.sub.2CH.sub.2--COOH group and a hydrogen atom, Y' is chosen
from --COOH and --CH.sub.2--CHOH--SO.sub.3H radicals, R.sub.5 is
chosen from alkyl radicals of an acid R.sub.5--COOH present in
coconut oil or in hydrolysed linseed oil, alkyl radicals, such as
C.sub.7, C.sub.9, C.sub.11 and C.sub.13 alkyl radicals, a C.sub.17
alkyl radical and its iso form, and unsaturated C.sub.17 radical.
These compounds are classified in the CTFA dictionary, 5th edition,
1993, under the names disodium cocoamphodiacetate, disodium
lauroamphodiacetate, disodium caprylamphodiacetate, disodium
capryloamphodiacetate, disodium cocoamphodipropionate, disodium
lauroamphodipropionate, disodium caprylamphodipropionate, disodium
capryloamphodipropionate, lauroamphodipropionic acid, and
cocoamphodipropionic acid. Salts of diethyl aminopropyl
cocoaspartamid can be also used.
The cationic surfactants may be chosen from: A) the quaternary
ammonium salts of general formula (VIII) below:
##STR00006## wherein X.sup.- is an anion chosen from halides
(chloride, bromide and iodide), (C.sub.2 C.sub.6)alkyl sulphates,
such as methyl sulphate, phosphates, alkyl and alkylaryl
sulphonates, and anions derived from organic acids, such as acetate
and lactate, and i) the radicals R.sub.1 to R.sub.3, which may be
identical or different, are chosen from linear and branched
aliphatic radicals comprising from 1 to 4 carbon atoms, and
aromatic radicals such as aryl and alkylaryl. The aliphatic
radicals can comprise at least one hetero atom such as oxygen,
nitrogen, sulphur and halogens. The aliphatic radicals are chosen,
for example, from alkyl, alkoxy and alkylamide radicals, R.sub.4 is
chosen from linear and branched alkyl radicals comprising from 16
to 30 carbon atoms. The cationic surfactant is, for example, a
behenyltrimethylammonium salt (for example chloride). ii) the
radicals R.sub.1 and R.sub.2, which may be identical or different,
are chosen from linear and branched aliphatic radicals comprising
from 1 to 4 carbon atoms, and aromatic radicals such as aryl and
alkylaryl. The aliphatic radicals can comprise at least one hetero
atom such as oxygen, nitrogen, sulphur and halogens. The aliphatic
radicals are chosen, for example, from alkyl, alkoxy, alkylamide
and hydroxyalkyl radicals comprising from about 1 to 4 carbon
atoms; R.sub.3 and R.sub.4, which may be identical or different,
are chosen from linear and branched alkyl radicals comprising from
12 to 30 carbon atoms, the said alkyl radicals comprise at least
one function chosen from ester and amide functions. R.sub.3 and
R.sub.4 are chosen, for example, from (C.sub.12
C.sub.22)alkylamido(C.sub.2 C.sub.6)alkyl and (C.sub.12
C.sub.22)alkylacetate radicals.
The cationic surfactant is, for example, a dicetyldimethyl ammonium
salt (for example chloride);
B)--the quaternary ammonium salts of imidazolinium, such as that of
formula (IX) below:
##STR00007## in which R.sub.5 is chosen from alkenyl and alkyl
radicals comprising from 8 to 30 carbon atoms, for example fatty
acid derivatives of tallow,
R.sub.6 is chosen from a hydrogen atom, C.sub.1 C.sub.4 alkyl
radicals and alkenyl and alkyl radicals comprising from 8 to 30
carbon atoms, R.sub.7 is chosen from C.sub.1 C.sub.4 alkyl
radicals, R.sub.8 is chosen from a hydrogen atom and C.sub.1
C.sub.4 alkyl radicals, and X.sup.- is an anion chosen from
halides, phosphates, acetates, lactates, alkyl sulphates, alkyl
sulphonates and alkylaryl sulphonates.
In one embodiment, R.sub.5 and R.sub.6 are, for example, a mixture
of radicals chosen from alkenyl and alkyl radicals comprising from
12 to 21 carbon atoms, such as fatty acid derivatives of tallow,
R.sub.7 is methyl and R.sub.8 is hydrogen. Such a product is, for
example, Quatemium-27 (CTFA 1997) or Quaternium-83 (CTFA 1997),
which are sold under the names "Rewoquat.RTM." W75, W90, W75PG and
W75HPG by the company Witco,
C)--the diquaternary ammonium salts of formula (X):
##STR00008## in which R.sub.9 is chosen from aliphatic radicals
comprising from about 16 to 30 carbon atoms, R.sub.10, R.sub.11,
R.sub.12, R.sub.13 and R.sub.14, which may be identical or
different, are chosen from hydrogen and alkyl radicals comprising
from 1 to 4 carbon atoms, and
X.sup.- is an anion chosen from halides, acetates, phosphates,
nitrates and methyl sulphates. Such diquaternary ammonium salts,
for example, include propanetallowdiammonium dichloride; and
D)--the quaternary ammonium salts comprising at least one ester
function, of formula (XI) below:
##STR00009## in which:
R15 is chosen from C1 C6 alkyl radicals and C1 C6 hydroxyalkyl and
dihydroxyalkyl radicals;
R16 is chosen from: a radical R19C(O)--, linear and branched,
saturated and unsaturated C1 C22 hydrocarbon-based radicals R20,
and a hydrogen atom, R18 is chosen from: a radical R21C(O)--,
linear and branched, saturated and unsaturated C1 C6
hydrocarbon-based radicals R22, and
a hydrogen atom, R17, R19 and R21, which may be identical or
different, are chosen from linear and branched, saturated and
unsaturated C7 C21 hydrocarbon-based radicals; n, p and r, which
may be identical or different, are chosen from integers ranging
from 2 to 6; y is chosen from integers ranging from 1 to 10; x and
z, which may be identical or different, are chosen from integers
ranging from 0 to 10; X-- is an anion chosen from simple and
complex, organic and inorganic anions; with the proviso that the
sum x+y+z is from 1 to 15, that when x is 0, then R16 is R20 and
that when z is 0, then R18 is R22.
In one embodiment, the ammonium salts of formula (XV) can be used,
in which:
R15 is chosen from methyl and ethyl radicals, x and y are equal to
1; z is equal to 0 or 1; n, p and r are equal to 2; R16 is chosen
from: a radical R19C(O)--, methyl, ethyl and C14 C22
hydrocarbon-based radicals, and a hydrogen atom; R17, R19 and R21,
which may be identical or different, are chosen from linear and
branched, saturated and unsaturated C7 C21, hydrocarbon-based
radicals; R18 is chosen from: a radical R21C(O)-- and a hydrogen
atom. Such compounds are sold, for example, under the names
Dehyquart by the company Cognis, Stepanquat by the company Stepan,
Noxamium by the company Ceca, and Rewoquat WE 18 by the company
Rewo-Witco.
Chelants
According to the present invention the compositions may comprise
chelants. Chelants are well known in the art and refer to a
molecule or a mixture of different molecules each capable of
forming a chelate with a metal ion. Chelants are well known in the
art and a non-exhaustive list thereof can be found in A E Martell
& R M Smith, Critical Stability Constants, Vol. 1, Plenum
Press, New York & London (1974) and A E Martell & R D
Hancock, Metal Complexes in Aqueous Solution, Plenum Press, New
York & London (1996) both incorporated herein by reference.
Examples of chelants suitable for use herein include EDDS
(ethylenediaminedisuccinic acid), carboxylic acids (in particular
aminocarboxylic acids), phosphonic acids (in particular
aminophosphonic acids) and polyphosphoric acids (in particular
linear polyphosphoric acids), their salts and derivatives.
Chelants may be incorporated into the composition of the present
invention as stabilizers and or preservatives. In addition it has
also been found that chelants provide hair fibre damage benefits
and thus they may be utilized in order to further improve the hair
damage profile of the present invention. Levels of chelants in the
present invention may be as low as about 0.1%, preferably at least
about about 0.25%, more preferably about 0.5% for the most
effective chelants such as diamine-N,N'-dipolyacid and monoamine
monoamide-N,N'-dipolyacid chelants (for example EDDS). Less
effective chelants will be more preferably used at levels of at
least about 1%, even more preferably above about 2% by weight of
the composition, depending of the efficiency of the chelant. Levels
as high as about 10% can be used, but above this level significant
formulation issues may arise.
Solvents
Suitable solvents for use in the compositions of the present
invention include, but are not limited to, water, butoxydiglycol,
propylene glycol, alcohol (denat.), ethoxydiglycol,
isopropylalcohol, hexylene glycol, benzyl alcohol and dipropylene
glycol.
Finally, the compositions according to the present invention can be
provided in any usual form, such as for example an aqueous
composition, a powder, a gel or an oil-in-water emulsion. A
preferred form for the compositions according to the present
invention are thickened solutions comprising a salt-tolerant
thickener or oil-in-water emulsions.
Method of Use
It is understood that the examples of methods of use and
embodiments described herein are for illustrative purposes only and
that various modifications or changes in light thereof will be
suggested to one skilled in the art without departing from the
scope of the present invention.
Oxidative hair dye compositions are usually sold in kits
comprising, in individually packaged components such as separate
containers, a dye component (also called "dye cream" for emulsions
or "dye liquid" for solutions) comprising the oxidative dye,
precursors and alkalizing agent which is typically ammonia in a
suitable carrier and; a hydrogen peroxide component (also called
"hydrogen peroxide cream" for emulsions or "hydrogen peroxide
liquid" for solutions) comprising the oxidizing agent (usually
hydrogen peroxide). The consumer mixes the dye component and
hydrogen peroxide component together immediately before use and
applies it onto the hair. The exemplified formulations given in the
tables hereinafter illustrate these resulting mixtures.
Similarly, bleaching compositions are also usually sold as a kit
comprising two or three individually packaged components typically
in two or three separate containers. The first component comprises
the ammonium ion source (e.g. ammonia), the second component
comprises the oxidizing agent and the third (optional) component
comprises a second oxidizing agent. The bleaching compositions are
obtained by mixing the above-mentioned compositions immediately
before use.
After working the mixture for a few minutes (to insure uniform
application to all of the hair), the oxidative dye composition is
allowed to remain on the hair for an amount sufficient for the
dyeing to take place (usually about 30 minutes). The consumer then
rinses his/her hair thoroughly with tap water and allows it to dry.
It is observed that the hair has changed from its original color to
the desired color.
When present in the oxidative dye compositions and bleaching
compositions, the optional conditioning agent can be provided in a
third container. In the latter case, all three compositions can be
mixed immediately before use and applied together, or the content
of the third container can be applied (after an optional rinse
step) as a post-treatment immediately after the oxidative dye
composition or bleaching composition resulting from the mixture of
the other containers.
For the oxidative hair dye compositions the radical scavenger may
be comprised within the dye component, or the hydrogen peroxide
component, or may be comprised as a separate radical scavenger
component, separately packaged. Similarly, for the bleaching
composition, the radical scavenger may be comprised within the
ammonium ion source component, the oxidising agent component, or
the second oxidising agent component, or within a separate radical
scavenger component, or comprised within two or more of the
components. Preferably, however the radical scavengers are
comprised within the dye component.
According to the present invention the radical scavengers may be
applied to the hair fibres at different time periods during the
hair treatment process. According to one method of treating hair
according to the present invention this comprises the steps of
separately applying a composition comprising at least one radical
scavenger and then applying an oxidising hair colouring composition
or separate compositions. The oxidizing hair colouring composition
or compositions may comprising at least one source of peroxyanion,
at least one alkalising agent and at least one source of carbonate,
carbamate and/or hydrogen carbonate ions. These steps may be
carried out in any order, preferably the radical scavenger
application step being carried out prior to the application of an
oxidizing hair colouring step. Preferably the oxidizing hair
colouring composition or compositions have a pH of up to 9.5 when
applied to the hair of the consumer, or have a pH that is up to 9.5
for at least about 50% of the time period the composition is
applied to the hair. Alternatively the individual compositions may
have varying pH levels such that on mixing or application to the
consumer the pH is up to 9.5.
Alternatively, the present invention also includes embodiments
wherein the method of treating the hair comprises applying a
composition comprising at least one oxidising agent, at least one
source of carbonate, carbamate, or hydrogen carbonate ions, at
least one alkalising agent and at least one radical scavenger, the
composition having a pH of up to 9.5, for at least about 50% of the
time period the composition is applied to the hair.
The kits described hereinabove are well known in the art and the
composition in each container can be manufactured utilizing any one
of the standard approaches, these include a) `Oil in water`
process, b) `Phase Inversion` process and c) `One-pot` process.
For example, in a `One-pot` process, the polymers and chelants
would be pre-dissolved in water, the fatty materials added and then
the whole composition heated to about 70 80.degree. C. A controlled
cooling and optional shearing process to form the final structured
product in the case of an emulsion would then follow. Addition of
the materials providing source of peroxymonocarbonate ions, radical
scavengers and ammonia, and optionally solvents, dyes and pH
trimming complete the making process of the dye cream.
In the case of a liquid solution comprising acrylate polymers,
these would be formulated into the hydrogen peroxide component. The
glycol solvents and fatty components are formulated into the dye
component. A structured product is formed when the dye and hydrogen
peroxide components are mixed together prior to use of the
composition, resulting from deprotonation of the polymer acrylic
acid groups as the pH rises, yielding a polymeric micro-gel.
Further details on the manufacture of these two-part aqueous
composition for coloring hair, which forms a gel on mixing of the
two parts can be found in U.S. Pat. No. 5,376,146, Casperson et al.
and U.S. Pat. No. 5,393,305, Cohen et al.
The composition of the present invention can also be formulated as
2-part aqueous compositions comprising polyetherpolyurethane as
thickening agent (such as Aculyn.RTM. 46) as described in U.S. Pat.
No. 6,156,076, Casperson et al. and U.S. Pat. No. 6,106,578,
Jones.
EXAMPLES
The following examples illustrate oxidative dye compositions
according to the present invention and methods of manufacture
thereof. It is understood that the examples and embodiments
described herein are for illustrative purposes only and that
various modifications or changes in light thereof will be suggested
to one skilled in the art without departing from the scope of the
present invention.
TABLE-US-00002 Examples of emulsion formulations 1 10 Formulation
Ingredient 1 2 3 4 5 6 7 8 9 10 Sodium sulphite 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 Ascorbic Acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
0.1 0.1 Ammonium Carbonate 3.0 6.0 2.0 -- 4.0 8.0 2.0 -- 4.0 6.0
Potassium Hydrogen -- -- 1.5 2.0 -- -- 2.0 2.0 -- -- Carbonate
Ammonium Acetate -- -- -- 2.0 -- -- -- 2.0 -- -- Ceteareth-25 1.0
-- -- -- -- -- -- 1.0 1.0 1.0 Steareth-100 -- 1.0 1.0 -- -- -- --
-- -- -- Sodium Palmytoyl -- -- -- -- 1.0 -- -- -- -- --
Sarcosinate Sodium Carboxymethyl -- -- -- 1.0 -- -- -- -- -- --
Lauryl Glucoside Sodium Lauryl Sulfate -- -- -- -- -- 1.0 -- -- --
-- Behentrimonium Chloride -- -- -- -- -- -- 1.0 -- -- -- Cetyl
Alcohol 1.6 -- 2 1.5 1.5 1.5 2.5 2.5 1.6 1.6 Stearyl Alcohol 3.3 --
2 1.5 1.5 1.5 2.5 2.5 3.3 3.3 Steareth-2 -- 5 1 -- -- -- -- -- --
-- Sodium Benzoate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Phenoxyethanol 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 EDTA
(tetrasodium salt) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sodium
Glycinate 2.0 5.0 3.0 1.0 -- -- -- -- -- 3.0 Glutamic Acid -- -- --
-- -- 6.0 2.0 -- -- -- Glycine -- -- -- 1.0 2.0 Glucosamine -- --
-- -- -- -- 2.0 4.0 4.0 3.0 Para-phenylene-diamine 0.8 0.5 0.6 0.5
0.8 0.8 0.5 0.6 0.5 0.8 Para-aminophenol 0.2 0.3 0.2 0.1 0.2 0.2
0.3 0.2 0.1 0.2 Meta-aminophenol 1.0 0.5 1.0 0.6 1.0 1.0 0.5 1.0
0.6 1.0 Resorcinol 1.6 1.2 1.6 0.8 1.6 1.6 1.2 1.6 0.8 1.6 Hydrogen
Peroxide 8.6 8.6 8.6 12.9 17 17 17 10.7 10.7 10.7 (35% active)
Amodimethicone 1.5 -- -- -- -- -- -- -- 1.0 -- (Belsil ADM1100)
Trimethylsilylamo- -- 0.5 -- -- -- -- -- 2.0 -- -- dimethicone
(SF1708) Polyquaternium-22 (Merquat -- -- 2.0 -- 0.1 -- -- -- -- --
295) Polyquaternium-37 & -- -- -- 0.5 0.1 -- -- -- -- --
Mineral oil (Salcare SC95) Polyquaternium 10 -- -- -- -- -- 0.2 0.2
-- -- -- (Polymer JR30M) Dicetyldimonium Chloride -- -- -- -- -- --
-- -- 0.2 -- Xanthan gum 0.1 0.5 -- -- 0.2 -- -- -- -- -- Cetyl
hydroxyethyl -- -- 0.8 -- -- -- -- -- -- -- Cellulose (Natrosol
330CS Plus) pH adjust to pH 9.0 qs qs qs qs qs qs qs qs qs qs Water
qs qs qs qs qs qs qs qs qs qs
TABLE-US-00003 Examples of emulsion formulations 11 20 Formulation
Ingredient 11 12 13 14 15 16 17 18 19 20 Sodium sulphite 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ascorbic Acid 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 Ammonium Carbonate 3.0 6.0 2.0 -- 4.0 8.0 2.0
-- 4.0 6.0 Potassium Hydrogen -- -- 1.5 2.0 -- -- 2.0 2.0 -- --
Carbonate Ammonium Acetate -- -- -- 2.0 -- -- -- 2.0 -- -- Crodafos
.RTM. CES 2.0 3.0 1.5 3.0 3.0 3.0 3.0 3.0 3.0 3.0 EDTA (tetrasodium
salt) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sodium Glycinate 2.0
5.0 3.0 1.0 -- -- -- -- -- 3.0 Glutaminc Acid -- -- -- -- -- 6.0
2.0 -- -- -- Glycine -- -- -- 1.0 2.0 -- -- -- -- -- Glucosamine --
-- -- -- -- -- 2.0 4.0 4.0 3.0 Para-phenylene-diamine 0.8 0.5 0.6
0.5 0.8 0.8 0.5 0.6 0.5 0.8 Para-aminophenol 0.2 0.3 0.2 0.1 0.2
0.2 0.3 0.2 0.1 0.2 Meta-aminophenol 1.0 0.5 1.0 0.6 1.0 1.0 0.5
1.0 0.6 1.0 Resorcinol 1.6 1.2 1.6 0.8 1.6 1.6 1.2 1.6 0.8 1.6
Hydrogen Peroxide 8.6 8.6 8.6 12.9 17 17 17 10.7 10.7 10.7 (35%
active) Amodimethicone 1.5 -- -- -- -- -- -- -- 1.0 -- (Belsil
ADM1100) Trimethylsilylamo- -- -- -- -- -- -- -- 2.0 -- --
dimethicone (SF1708) Polyquaternium-22 (Merquat -- -- 2.0 -- 0.5 --
-- -- -- -- 295) Polyquaternium-37 & -- -- -- 0.5 0.1 -- -- --
-- -- Mineral oil (Salcare SC95) Polyquaternium 10 -- -- -- -- --
0.2 0.2 -- -- -- (Polymer JR30M) Dicetyldimonium Chloride -- -- --
-- -- -- -- -- 0.2 -- Xanthan gum 0.1 -- 0.2 0.2 -- -- -- -- -- --
Succinoglycan -- -- -- -- 0.2 0.5 -- -- -- -- Carbomer -- -- -- --
-- -- 1.0 0.5 -- -- Acrylates/C10 30 Alkyl -- -- -- -- -- -- -- 0.5
-- -- Acrylate Crosspolymer Hydroxyethyl cellulose -- -- -- -- --
-- -- -- 0.5 -- Hydroxypropyl Starch -- -- -- -- -- -- -- -- -- 2.0
Phosphate pH adjust to pH 9.0 qs qs qs qs qs qs qs qs qs qs Water
qs qs qs qs qs qs qs qs qs qs
TABLE-US-00004 Examples of thickened aqueous solution formulations
1 10 Formulation Ingredient 1 2 3 4 5 6 7 8 9 10 Sodium sulphite
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ascorbic Acid 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 Citric Acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0
1.0 1.0 1.0 Ammonium Carbonate 3.0 6.0 2.0 -- 4.0 8.0 2.0 -- 4.0
6.0 Potassium Hydrogen -- -- 1.5 2.0 -- -- 2.0 2.0 -- -- Carbonate
Ammonium Acetate -- -- -- 2.0 -- -- -- 2.0 -- -- Oleth 10 1.0 1.0
1.0 1.0 -- -- -- -- -- -- Oleth 2 0.8 0.8 0.8 0.8 -- -- -- -- -- --
Oleic Acid 0.9 0.9 0.9 0.9 -- -- -- -- -- -- Cocamide DEA 3.0 3.0
3.0 3.0 -- -- -- -- -- -- EDTA(tetrasodium salt) 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 Sodium Glycinate 2.0 5.0 3.0 1.0 -- -- --
-- -- -- Glutaminc Acid -- -- -- -- -- 6.0 2.0 -- -- -- Glycine --
-- -- 1.0 2.0 -- -- -- -- -- Glucosamine -- -- -- -- -- -- 2.0 4.0
4.0 3.0 Para-phenylene 0.8 0.5 0.6 0.5 0.8 0.8 0.5 0.6 0.5 0.8
Diamine Para-aminophenol 0.2 0.3 0.2 0.1 0.2 0.2 0.3 0.2 0.1 0.2
Meta-aminophenol 1.0 0.5 1.0 0.6 1.0 1.0 0.5 1.0 0.6 1.0 Resorcinol
1.6 1.2 1.6 0.8 1.6 1.6 1.2 1.6 0.8 1.6 Hydrogen Peroxide 8.6 8.6
8.6 13 17 17 17 10.7 10.7 10.7 (35% active) Polyquaternium-22
(Merquat -- -- -- -- 0.5 -- -- -- -- -- 295) Polyquaternium-37
& Mineral -- -- -- -- 0.1 -- 0.5 -- -- -- oil (Salcare SC95)
Amodimethicone -- -- -- -- -- 1.0 -- -- -- -- (Belsil ADM1100)
Acrylates Copolymer 2.4 2.4 2.4 2.4 -- -- -- -- -- -- (Aculyn .RTM.
33A) Acrylates Steareth-20 0.5 0.5 -- 1.0 -- -- -- -- -- --
Methacrylate Copolymer (Aculyn .RTM. 22) Xanthan gum -- -- -- -- --
1.0 -- -- -- -- Succinoglycan -- -- -- -- 0.8 -- -- -- -- --
Carbomer -- -- -- -- -- -- 2.0 -- -- Acrylates/C10 30 Alkyl -- --
-- -- -- -- -- 2.0 -- -- Acrylate Crosspolymer Hydroxyethyl
cellulose -- -- -- -- -- -- -- -- 2.0 -- Hydroxypropyl Starch -- --
-- -- -- -- -- -- -- 2.0 Phosphate Propylene Glycol 8.2 8.2 8.2 8.2
8.0 8.0 8.0 8.0 8.0 8.0 Ethoxy Diglycol 4.2 4.2 4.2 4.2 -- -- -- --
-- -- pH adjust to pH 9.0 qs qs qs qs qs qs qs qs qs qs Water qs qs
qs qs qs qs qs qs qs qs
The above compositions are useful for dyeing hair with reduced
damage. Similar compositions not including oxidative dye precursors
and couplers (in the above examples para-aminophenol,
meta-aminophenol and resorcinol) can be used for bleaching
(lightening) hair.
Test Protocols Calculation of the Charge Transfer Energy
The molecular structure of all the species involved in the charge
transfer reaction (reactants and products) is optimised using the
software MOPAC2002 version 2.2 implemented in the molecular
modelling package FUJITSU CA Che version 6.1. to minimise the
energy (J. J. P. Stewart, Fujitsu Limited, Tokyo, Japan (1999)).
The structural optimisation is based on the quantum mechanic method
known as "semi-empirical" method Austin Model 1 (AM1. (M. J. S.
Dewar et al. J. Am. Chem. Soc. 107, 3902 3909 (1985)).
The heat of formation (.DELTA.H.sub.f) calculated by MOPAC is the
energy used or released on molecule formation relative to elements
in the standard state at 25.degree. C. The heat of formation of
non-radical species (Scav and CO.sub.3.sup.2-) is calculated using
the Restricted Hartree Fock (RHF) scheme. The heat of formation
(.DELTA.H.sub.f) of chemical species with an odd number of
electrons, e.g. the radical species Scav*.sup.+ and
CO.sub.3*.sup.-, is calculated using the Unrestricted Hartree Fock
(UHF) scheme.
The solvation effect of water on all chemical species involved is
taken into account using the solvation method COSMOI
(COnductor-like Screening MOdel) implemented in CAChe. (A. Klamt
and G. Schuumann. J. Chem. Soc. Perkin Transactions 2, 799 805,
(1993)). In order to confirm that the molecular structure of all
species has been truly optimised, the Infrared vibrational spectrum
is computed: the absence of negative frequency indicating that the
true minimum has been reached.
The heat of formation of all chemicals is then calculated following
the above procedure, and is used to calculate the energy of the
charge transfer reaction. Values obtained for a number of radical
scavengers is given below:
TABLE-US-00005 Radical Scavenger .DELTA.E Reaction Radical
Scavenger .DELTA.E Reaction 2-amino-propanol 9.2 Glutamic acid 6.8
Benzylamine 8.6 Piperidine 4.3 Ethanolamine 7.8 Morpholine 1.9
Piperdine 4.3 Sarcosine 2.3
Test Assessing Protocols
Two different test methods were used to assess the benefits
conferred to hair by the compositions according to the present
invention. These methods (Instron combing and Tensile testing) are
described in detail below.
For each composition tested, switches of human virgin dark hair
were used. "Virgin hair" means hair that has never been treated
chemically and can be bought, for example, at Hugo Royer
International Ltd, 10 Lakeside Business Park, Swan Park, Sandhurst,
Berkshire, GU47 9ND. They were treated stepwise according to the
following protocol.
A bleaching composition comprising the composition to be tested is
prepared by mixing in equal weight amounts a hydrogen peroxide
emulsion base composition and a dye emulsion base composition
(pH=9.0). No dyes were added to the tint emulsion base composition
allowing for the measurement of the lightening achieved.
The hydrogen peroxide emulsion base composition contains: a) 35% by
weight of an emulsion base premix comprising 10% stearyl alcohol
and 5% cetereth25; b) 25% of an stabilizing solution comprising 1%
tetrasodium DTPA, 0.4% HEDP, 1% sodium hydroxide (32% purity) and
water q.s. c) 14% of water; d) 26% of a solution of hydrogen
peroxide (35% purity). The dye emulsion base composition contains:
a) 0.2% by weight of sodium sulphite; b) 0.2% of ascorbic acid; c)
44.5% of the same emulsion base premix used for the hydrogen
peroxide emulsion base; d) 6% of ammonium carbonate e) The amount
to be tested of the radical scavenger or mixture of radical
scavengers. f) pH adjustment to pH=9.0 with sodium hydroxide g)
q.s. of water.
A reference bleaching composition is also prepared. This
composition comprises an equal amount of the mixture of the
hydrogen peroxide emulsion base composition described herein above
and a tint emulsion base composition as for the tested composition
described hereinabove with the exception that the 6% ammonium
carbonate is replaced with 8% ammonium hydroxide and the pH is
adjusted to pH=10.0.
2 g of the bleaching composition to be tested per g of hair to be
treated was applied on the hair switches and massaged in
thoroughly. The hair switches were then wrapped in a plastic film
removed and put in an oven at 30.degree. C. After 30mins, they were
removed from the oven and from the wrapping film and rinsed for
Imin, in water, (tap water with a hardness of 9 grains/gallon). 0.1
g of shampoo per g. of hair was then added and milked for 30s at a
rate of at least 150 strokes a minute before rinsing for 30 s. The
application of shampoo was repeated and the hair then left to dry
at ambient temperature.
Instron Combing Procedure
The virgin hair used was prepared into switches of 6 grams in
weight and 10 inches in length. The switches were treated with the
emulsion formulations as above for one cycle. The switches were
treated before measuring.
The equipment used for the test was an Instron 5500 series Tensile
Tester with an attachment for Instron Combing (custom made) and an
Instron Static Load Cell, rated 10N. The switches were mounted on
the instrument and the force required to comb the switches
measured. The extension speed was 15 mm/sec, the extension length
was 240 mm and the reading time interval was 0.5 sec. In all
experiments at least 5 readings were performed on each switch and
at least 10 switches were used for each treatment.
Tensile Tester
The virgin hair used was prepared into switches of 1.5 grams in
weight and 6.0 inches in length.
The switches were treated with the emulsion formulations as above
for three repeat cycles. The equipment used for the test was a
Diaston Miniature Tensile Tester MTT670. Hair strands from both
untreated hair and treated hair are cut from the appropriate hair
switch and placed on a clean surface ensuring all fibres are
running in the same direction of root to tip. Single fibres are
then threaded through two brass ferrules and clamped in place. The
fibres are then mounted on the Diastron Miniature Tensile Tester
MTT670 carousel in groups of 10 alternating between treated fibres
and untreated fibres to a total of 100 fibres (50 fibres untreated
and 50 fibres treated). Before commencing the experimental run the
samples are doused in di-ionised water ensuring the fibres are
completely immersed in water.
The samples are run on the Diastron Miniature Tensile Tester
according to the standard operating procedure and the stress-strain
curve obtained. For details of the stress-strain curves and the
tensile method see Clarence R Robbins, Chemical & Physical
Behavior of Human Hair, 3.sup.rd Ed, Springer-Verlag, 1994, p300.
The results for the treated and untreated fibres were compared via
a multi-factor Anova statistics and presented verses the untreated
fibres.
Lightening Test
The lightening was measured using a Minolta CM3600D
Spectrophotometer. Eight readings were taken on each switch and an
average of 3 switches was measured. The dL value was calculated as
the L value after treatment minus the L value of virgin hair.
Ammonia Odour Test
The ammonia odour is assessed by a qualified perfumer as described
below. Using 2 g of test composition to 1 g of hair, 30 g of test
composition colourant was applied to the hair switch. The
composition was applied with a syringe using a zigzag action down
the length of the hair switch. The odour intensity and character
were evaluated and scored according to the following scale: 5--No
ammonia, 4--Slight ammonia, 3--Moderate ammonia, 2--Strong ammonia,
1--Extremely strong ammonia and 0--overwhelming ammonia
Test Results
TABLE-US-00006 TABLE 1 Instron Combing Force* (mJ) Ammonia
Lightening Composition Av. Std. Dev Odour (dL) Reference
composition: 455.4 158.8 3 10 (4.5% hydrogen peroxide pH = 10.0)
Invention composition: 215.7 35.7 5 10 (3% Ammonium carbonate, 3%
glucosamine & 4.5% hydrogen peroxide pH = 9.0) *One cycle
treatment. 50 data points per treatment - high standard deviation
for current colourant product due to high combing force.
Significant to 99% confidence.
TABLE-US-00007 TABLE 2 15% Force To Extension Break Radical Force
Fibre Lightening Treatment Scavenger (gmf) (gmf) (dL) Untreated
virgin Hair -- 20.3 72.7 -- Reference composition None 12.5 S 46.1
15 (3% Ammonium Carbonate, S 4.5% Hydrogen Peroxide) 3% Ammonium
Carbonate, 6% 18.1 s 72.6 15 4.5% Hydrogen Peroxide Sodium
Glycinate 3% Ammonium Carbonate & 6% 18.9 77.2 15 4.5% Hydrogen
Peroxide Glutamine 3% Ammonium Carbonate & 6% 17.0 s 67.8 15
4.5% Hydrogen Peroxide Arginine s = significant verses untreated
hair to 95% confidence, S = significant verses untreated hair to
99% confidence.
From the above test results it can be clearly observed that the
formulations according to the present invention deliver the
required lightening whilst causing less fibre damage and malodour
during application.
All documents cited in the Detailed Description of the Invention
are, in relevant part, incorporated herein by reference; the
citation of any document is not to be construed as an admission
that it is prior art with respect to the present invention.
While particular embodiments of the present invention have been
illustrated and described, it would be obvious to those skilled in
the art that various other changes and modifications can be made
without departing from the spirit and scope of the invention. It is
therefore intended to cover in the appended claims all such changes
and modifications that are within the scope of this invention.
* * * * *